High temperature material compositions for high temperature thermal cutoff devices

ABSTRACT

The present disclosure provides a high-temperature thermal pellet composition that maintains structural rigidity up to a transition temperature of about 240° C. The composition comprises at least one organic compound (e.g., triptycene or 1-aminoanthroquinone). The pellet can be disposed in a housing of a thermally-actuated, current cutoff device, such as a high-temperature thermal cutoff device (HTTCO). Also provided are material systems, which include the pellet composition and a high-temperature seal that provides substantial sealing up to at least the transition temperature. Methods of making such high-temperature pellet compositions and incorporating them into a thermally-actuated, current cutoff device are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 12/512,369 filed on Jul. 30, 2009, which claims the benefit ofU.S. Provisional Application No. 61/086,330, filed on Aug. 5, 2008. Theentire disclosures of each of the above applications are incorporatedherein by reference.

FIELD

The present disclosure relates to high temperature material compositionsfor electrical current interruption devices and more particularly topellet compositions and materials for high-temperature electricalcurrent interruption safety devices, or thermal cut-offs, that provideprotection from over-temperature conditions.

BACKGROUND

The statements in this section merely provide background informationrelated to the present disclosure and may not constitute prior art.

Temperatures of operation for appliances, electronics, motors and otherelectrical devices typically have an optimum range. The temperaturerange where damage can occur to system components or where the devicebecomes a potential safety hazard in the application or to the end-userserves as an important detection threshold. Various devices are capableof sensing such over-temperature thresholds. Certain devices which arecapable of sensing over-temperature conditions and interruptingelectrical current include electrical thermal fuses, which only operatein a narrow temperature range. For example, tin and lead alloys, indiumand tin alloys, or other metal alloys which form a eutectic metal, areunsuitable for appliance, electronic, electrical and motor applicationsdue to undesirably broad temperature response thresholds and/ordetection temperatures that are outside the desired range of safety.

One type of device particularly suitable for over-temperature detectionis an electrical current interruption safety device, known as a thermalcut-off (TCO), which is capable of temperature detection andsimultaneous interruption of current, when necessary. Such TCO devicesare typically installed in an electrical application between the currentsource and electrical components, such that the TCO is capable ofinterrupting the circuit continuity in the event of a potentiallyharmful or potentially dangerous over-temperature condition. TCOs areoften designed to shut off the flow of electric current to theapplication in an irreversible manner, without the option of resettingthe TCO current interrupting device. High temperature appliances andapplications require the use of robust over-temperature detectiondevices with high-holding temperatures exceeding the operatingtemperatures and/or holding temperatures of conventional TCO designs.Thus, in various aspects, the present disclosure provides stable,reliable, and robust high-temperature TCO devices.

DRAWINGS

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

FIG. 1 is an enlarged cross sectional view of an exemplary thermalcutoff device construction;

FIG. 2 illustrates the thermal cutoff construction of FIG. 1 after athermal pellet has undergone a physical transition and a currentinterruption actuating assembly has caused electrical switching to breakcontinuity and change the thermal cutoff device's operating condition;

FIG. 3 is a side perspective view illustrating a high-temperaturethermal pellet according to certain aspects of the present disclosure;

FIG. 4 is a side view of a sliding contact member of the currentinterruption actuating assembly switch construction of FIG. 1;

FIG. 5 is a side view of one of the springs of the current interruptionactuating assembly of FIG. 1;

FIG. 6 is a cross sectional view of a ceramic bushing of FIG. 1; and

FIG. 7 is an elevation view of a thermal cutoff device of FIG. 1.

DETAILED DESCRIPTION

The following description is merely exemplary in nature and is notintended to limit the present disclosure, application, or uses.

Various safety electrical current interruption devices, includingthermal cut-off electrical current interruption safety devices (TCOs),meet a broad range of application temperatures and break electricalcurrent above a threshold temperature or rating, typically ranging fromabout 60° C. up to about 235° C. However, conventional TCO devices arenot rated for higher temperature applications, such as those greaterthan or equal to about 240° C. In other words, conventional TCO deviceshave not sufficiently fulfilled the performance criteria, particularlystability and robustness, for long-term use in high-temperatureapplications as a safety device.

In various aspects, the present disclosure provides a high temperaturethermal cutoff device (referred to herein as a “HTTCO”). Such an HTTCOdevice is capable of switching continuity of an electrical circuit orelectrical communication when the surrounding environment or operatingtemperature reaches a predetermined threshold temperature. By use of theterm “high-temperature” thermal cutoff device, it is meant that devicehas a threshold or actuation temperature of greater than about 235° C.,optionally greater than or equal to about 240° C., optionally greaterthan or equal to about 245° C., optionally greater than or equal toabout 250° C., optionally greater than or equal to about 255° C.,optionally greater than or equal to about 260° C., optionally greaterthan or equal to about 265° C., optionally greater than or equal toabout 270° C., optionally greater than or equal to about 275° C.,optionally greater than or equal to about 280° C., optionally greaterthan or equal to about 285° C., optionally greater than or equal toabout 290° C., optionally greater than or equal to about 295° C.,optionally greater than or equal to about 300° C., and in certainaspects, greater than or equal to about 305° C. In certain aspects, theHTTCO exhibits switching behavior at a threshold or actuationtemperature of greater than or equal to about 240° C. to less than orequal to about 270° C., optionally greater than or equal to about 240°C. to less than or equal to about 265° C., optionally greater than orequal to about 240° C. to less than or equal to about 260° C.,optionally greater than or equal to about 240° C. to less than or equalto about 255° C., optionally greater than or equal to about 240° C. toless than or equal to about 250° C., optionally greater than or equal toabout 240° C. to less than or equal to about 245° C., optionally greaterthan or equal to about 240° C. to less than or equal to about 243° C. Incertain aspects, the HTTCO exhibits switching behavior at a thresholdtemperature of about 240° C., optionally about 241° C., optionally about242° C., optionally about 243° C., optionally about 244° C., optionallyabout 245° C., optionally about 246° C., optionally about 247° C.,optionally about 248° C., optionally about 249° C., optionally about250° C., optionally about 251° C., optionally about 252° C., optionallyabout 253° C., optionally about 254° C., optionally about 255° C.,optionally about 256° C., optionally about 257° C., optionally about258° C., optionally about 259° C., optionally about 260° C., optionallyabout 261° C., optionally about 262° C., optionally about 263° C.,optionally about 264° C., optionally about 265° C., optionally about266° C., optionally about 267° C., optionally about 268° C., optionallyabout 269° C., and in certain embodiments, optionally about 270° C.

An illustrative test demonstrating the performance of a high temperaturethermal pellet composition includes continuous aging of HTTCO devicesformed in accordance with the present teachings for at least 1,000 hoursat a sustained temperature of 235° C. While the HTTCO ideally meets orexceeds the aforementioned illustrative test protocol, it should beunderstood by those skilled in the art that the compositions arecontemplated as being useful for both low voltage and high voltageapplications. Further, in certain aspects, the high temperature thermalpellet compositions meet or exceed Underwriters' Laboratory test UL1020or IEC/EN 60691 standards, which are respectively incorporated herein byreference. In certain embodiments, HTTCO devices meet one or more ofsuch standards at the pre-selected high temperature rating for thedevice. While the performance criteria is fully outlined in each ofthese standards, salient aspects of performance tests that demonstrateconformance to the IEC 60691, Third Edition standard are summarized inTable 1.

TABLE 1 IEC 60691, 3^(rd) Edition Tests I Clause 7 Ink Rub Test: A Rubtest sample with a cotton “wheel” soaked in water. B Take a photo. CAfter tensile, thrust, temperature/ humidity, transient over load,temperature check, and dielectric/insulation testing repeat steps A andB. II Clause 9.2 Tensile (pull) Test: A Place sample in the fixture andapply 3.7 lbs tensile for one minute. B Release force and remove. IIIClause 9.3 Thrust (push) Test: A Place sample in the fixture and apply0.9 lbs thrust for one minute. B Release force and remove IV Clause 9.4Twist/Bend Test: A Bend contact lead 90°, twist lead 180°, and check forepoxy breakage. V Clause 10.2 Temperature/ Humidity Test: A Samples aresubjected to two complete conditioning cycles: i 24 hours at ratedfunctioning temperature minus 15° C.; ii 96 hours at 35° C. (+/−2°) and95% R.H. (+/−5 R.H.); iii 8 hours AT 0° C. (+/−2°). B Samples aresubjected to a third complete conditioning cycle: i 24 hours at ratedfunctioning temperature minus 15° C.; ii 168 hours at 35° C. (+/−2°) and95% R.H. (+/−5 R.H.); iii 8 hours AT 0° C. (+/−2°). VI Clause 10.6Current Interrupt Test: A Sample is placed in a kiln at ratedfunctioning temperature minus 10° C. for three minutes. B Sample istested at 110% of rated voltage and 150% of rated current until sampleinterrupts the test current. VII Clause 10.7 Transient Overload (pulse)Test: A Samples are place in the current path of D.C. current pulses,with an amplitude of 15 times rated current for a duration of 3 ms with10 s intervals are applied for 100 cycles. VIII Clause 11.2 TemperatureCheck (T_(f)): A Samples are placed in an oven at rated functioningtemperature minus 10° C. until stable, the temperature is then increasedsteadily at 0.5° C./minute until all samples are opened, recording thetemperature of opening to pass +0/−5° C. IX Clause 11.3 MaximumTemperature (T_(m)): A Samples are placed in a kiln at a specifiedtemperature (470° C. +0/−5° for a 257° C. TCO) for 10 minutes, with thesamples maintained at T_(m) a dielectric test at 500 Vac with nobreakdown, and an insulation resistance test at 500 Vdc with a minimumof 0.2 MΩ. X Clause 11.4 Aging: A Samples are placed in a kiln at 200°C. for three weeks. At the conclusion of this test at least 50% ofsamples shall not have functioned. B Samples are then placed in a kilnat rated functioning temperature minus 15° C. for three weeks. At theconclusion of this test at least 50% of samples shall not havefunctioned. C Samples are then placed in a kiln at rated functioningtemperature minus 10° C. for two weeks. D Samples are then placed in akiln at rated functioning temperature minus 5° C. for one week. ESamples are then placed in a kiln at rated functioning temperature minus3° C. for one week. F Samples are then placed in a kiln at ratedfunctioning temperature plus 3° C. for 24 hours. G This test isconsidered successful if all samples have functioned at the conclusionof step X(F). XI Clause 10.3/10.4 Room Temperature Dielectric andInsulation Resistance: A All test samples must complete and comply witha dielectric test at 500 Vac with no breakdown, and an insulationresistance test at 500 Vdc with a minimum of 0.2 MΩ.

In various aspects, the HTTCO of the present disclosure comprises asealed housing having disposed therein a high-temperature thermal pellethaving a transition temperature of greater than or equal to about 240°C. The transition temperature of the high-temperature thermal pelletrelates to the threshold temperature at which the HTTCO device switchesor actuates, as will be described in greater detail below. Thehigh-temperature thermal pellet comprises at least one organic compound,which generally has a melting point or melting point range near thepre-selected or desired transition temperature. Further, the HTTCO has ahigh-temperature seal disposed in a portion of at least one opening ofthe housing that substantially seals the housing up to the transitiontemperature of the high-temperature thermal pellet. The HTTCO alsocomprises a current interruption assembly that is at least partiallydisposed within the housing. The current interruption assemblyestablishes electrical continuity in a first operating condition of theHTTCO, which corresponds to an operating temperature of less than thetransition temperature of the high-temperature thermal pellet and thatdiscontinues electrical continuity when the operating temperatureexceeds the transition temperature.

An exemplary high-temperature TCO device is described herein, as setforth in FIGS. 1 and 2. In general, a TCO 10 includes a conductivemetallic housing or casing 11 having a first metallic electricalconductor 12 in electrical contact with a closed end 13 of the housing11. An isolation bushing 14, such as a ceramic bushing, is disposed inan opening 15 of the housing 11. Housing 11 further includes a retaineredge 16, which secures the ceramic bushing 14 within the end of thehousing 11. An electric current interrupter assembly for actuating thedevice in response to a high temperature, for example, by breakingcontinuity of an electrical circuit, includes an electric contact 17,such as a metallic electrical conductor, at least partially disposedwithin the housing 11 through opening 15. Electric contact 17 passesthrough isolation bushing 14 and has an enlarged terminal end 18disposed against one side 19 of isolation bushing 14 and a second end 20projecting out of the outer end 21 of isolation bushing 14. Ahigh-temperature seal 28 is disposed over the opening 15 and can createsealing contact with the housing 11 and its retainer edge 16, theisolation bushing 14, and the exposed portion of the second end 20 ofelectric contact 17. In this manner, an interior portion 29 of thehousing 11 is substantially sealed from the external environment 30. By“substantially sealed” it is meant that the while the barrier seal isoptionally porous at a microscopic level, the barrier is capable ofpreventing escape or significant mass loss of the thermal pelletmaterial, for example, the seal retains at least about 95% of the massof the initial thermal pellet through 1,000 hours of continuousoperation at 235° C., optionally about 96% of the mass of the initialthermal pellet, optionally greater than about 97% of the mass of theinitial thermal pellet, optionally greater than or equal to about 98% ofthe mass of the initial thermal pellet, optionally greater than or equalto about 99% of the mass of the initial thermal pellet, optionallygreater than or equal to about 99.5% of the mass of the initial thermalpellet and in certain aspects, greater than or equal to about 99.9% ofthe mass of the initial thermal pellet is retained within the housingthrough continuous operation.

The current interruption assembly, which actuates or switches to changecontinuity of an electrical circuit, further includes a sliding contactmember 22, formed of electrically conductive material, such as a metalis disposed inside the housing 11 and has resilient peripheral fingers23 (FIG. 4) disposed in sliding engagement with the internal peripheralsurface 24 of the housing 11 to provide electrical contact therebetween. Moreover, when the TCO has an operating temperature that isbelow the predetermined threshold set-point temperature of the TCOdevice, the sliding contact member 22 is disposed in electrical contactwith the terminal end 18 of electric contact 17.

Current interruption assembly also includes a tensioning mechanism,which may include a plurality of tensioning mechanisms. The tensioningmechanism biases the sliding contact member 22 against the terminal end18 of electric contact 17 to establish electrical contact in the firstoperating condition (where operating temperatures are below thethreshold temperature of the TCO device, as will be described below). Asshown in FIGS. 1 and 2, the tensioning mechanism includes a pair ofsprings, which are respectively disposed on opposite sides of thesliding contact member 22. The springs include a compression spring 26and an expansion trip spring 27.

A high-temperature thermally responsive pellet or thermal pellet 25, asbest illustrated in FIG. 3, is disposed in the housing 11 against theend wall 13 thereof. The compression spring 26 is in a compressed statebetween the high-temperature solid thermal pellet 25 and the slidingcontact member 22 and in the exemplary design shown, generally has astronger compressed force than the force of the expansion trip spring27, which is disposed between the contact member 22 and the isolationbushing 14, such that the sliding contact member 22 is biased towards(e.g., held by the force of the spring 26) and in electrical contactwith the enlarged end 18 of the electrical contact 17. In this manner,an electrical circuit is established between the first electricalconductor 12 and electrical contact 17 through the conductive housing 11and sliding contact member 22.

As noted above, the TCO device is designed to include a high-temperaturethermal pellet 25 that is reliably stable in the first operatingcondition (where the operating temperature, for example, the temperatureof the surrounding environment 30 is below a threshold temperature);however reliably transitions to a different physical state when theoperating temperature meets or exceeds such threshold temperature in asecond operating condition. In such conditions, where the operatingtemperature meets or exceeds a threshold temperature, thehigh-temperature thermal pellet 25 melts, liquefies, softens,volatilizes, or otherwise transitions to a different physical stateduring an adverse heating condition, which is illustrated in FIG. 2.

The springs 26 and 27 are adapted to expand and release, as illustratedby expansion trip spring 27 in FIG. 5, and through the relationship ofthe particular forces and length of the compression spring 26 andexpansion trip spring 27, the sliding contact member 22 is moved out ofelectrical contact with the end 18 of the electric contact 17 in themanner shown in FIG. 2, so that the electrical circuit between theterminal conductor 12 and electrical contact 17 through the thermalcutoff construction 10 (via the housing 11 and sliding contact member22) is discontinued and broken, remaining open as illustrated in FIG. 2.

The thermal cutoff device described in the present disclosure are usedfor purposes of illustration are exemplary and in certain aspects,should not be construed to be limiting. In certain aspects, variouscomponents, designs, or operating principles may be varied in number ordesign. Various other thermal switching or cutoff devices are known inthe art and likewise contemplated.

In various aspects, the high-temperature thermal pellet compositions ofthe present teachings are thermally and chemically stable, reliable, androbust for use in the HTTCO application. Preferably, thehigh-temperature thermal pellet composition will include one or moreorganic compounds, such as crystalline organic compounds. In variousaspects, the high-temperature thermal pellet compositions are designedto have a transition temperature that permits the HTTCO device to have afinal temperature (T_(f)) (also referred to as actuation or thresholdtemperature) where the internal contact breaks electrical continuity dueto structural changes in the pellet composition, which in turn causesopening of tensioning mechanisms, for example. Thus, the transitiontemperature of the high-temperature thermal pellet directly correspondsto the threshold temperature T_(f) of the HTTCO device, whereby a switchin continuity is activated. As noted above, the transition temperaturegenerally refers to the temperature at which a pellet melts, liquefies,softens, volatilizes, sublimates, or otherwise transitions to adifferent physical state to transform from a solid having structuralrigidity to a form or phase that loses structural rigidity, either bycontraction, displacement, or other physical changes, which cause theinternal electrical contacts to separate due to the applied tension fromthe tensioning mechanism. Thus, as used herein, once the thermal pelletmaterial reaches it transition temperature, it means that the materialno longer possesses the structural integrity required to maintain atensioning mechanism, such as a switch in a held-open or held-closedposition, depending on the HTTCO device, for example.

As referred to herein, this transition temperature is also referred toas a “melting-point”; however, the compounds in the pellet compositionneed not fully melt in a conventional sense to achieve separation of theelectrical contacts to break the internal circuit and electricalcontinuity. As recognized by those of skill in the art, a melting-pointtemperature is one where compounds or compositions transform from solidto liquid phase, which may occur at a range of temperatures, rather thanat a single discrete temperature point. In certain aspects, the hightemperature thermal pellet may soften or sublimate rather than melting,by way of non-limiting example, to achieve the separation of electricalcontacts to break the circuit. Melting-point temperatures can bemeasured in various apparatuses, such as those produced by ThomasHoover, Mettler and Fisher-Johns companies. Differential ScanningColorimetry (DSC) techniques are also commonly used. Differentmeasurement techniques may result in differing melting points, forexample, optical analysis methods like Fisher-Johns measure lighttransmittance through a sample, a solid to liquid phase change. Earlyoptical methods potentially suffered greater observer error versus moremodern light beam transmittance melt point indicators. In addition,earlier techniques to determine melting point (before the use of digitalhigh speed scan capabilities), rendered a broader range of results formelt points and other transitions. Likewise, before the advent of HPLCand other precise analytical techniques for determination of purity, themelt point of a sample, for example, measured by DSC, which measuresheat flow behavior for example, crystallinity (solid-solid phase)changes as well as, solid to liquid phase changes, could show thesolid-solid phase change of an impurity that may have been reported as amelt point, such as dehydration or breaking of hydroxyl bonds, as wellas the solid-liquid phase change at the melt point for the material ofinterest. Thus, in various aspects, a composition can be selected foruse in the thermal pellet that empirically exhibits a desirable physicalchange that will enable a pellet's physical transition withoutnecessarily correlating to the predicted melting point ranges.

In certain aspects, the high-temperature thermal pellet 25 has arelatively rapid and repeatable collapse rate, meaning once theenvironment 30 reaches a threshold temperature, the rate at which thehigh-temperature thermal pellet composition 25 physically collapses isrelatively high. By way of example, one method of testing a pelletcollapse rate is via thermomechanical analysis (TMA) where a pellet isheated at a rapid rate to within about 10° C.-15° C. of the predictedmelting point temperature, then a heating rate is selected, for exampleabout 0.5° C./min through the predicted melting point temperature range.The physical height of the pellet is likewise measured at the beginningof the test and throughout this heating process, so that an amount ofdisplacement from the top surface of the pellet to the underlyingsubstrate (on which the pellet is initially placed) is measured. Therate, measured in micrometer per ° C., at which the pellet heightcollapses at the onset through to the end of the transition temperaturecorrelates to the pellet collapse rate, for example, a 75% reduction ofa pellet's height from a threshold temperature within about 100micrometer/° C., optionally about 500 micrometer/° C., optionally about1000 micrometer/° C. In various aspects, both the solid liquid phasetransition temperature and pellet collapse rate are salient features ofthe high-temperature thermal pellet 25, as the rapidity with which thepellet collapses ensures sufficient separation of electrical contacts inthe HTTCO to avoid excessive arcing, which could melt various componentsand potentially impact HTTCO performance. Methods of testing andquantifying such a pellet collapse rate will be described in furtherdetail below.

In certain aspects, the thermal pellet comprises one or more organiccompounds having a melting-point temperature (mp) that occurs in a rangeof temperatures corresponding to the desired transition temperature. Byway of example, in certain aspects, the high-temperature thermal pellethas one or more organic compounds that have a melting point temperature(mp) within about 5° C. below the transition temperature and withinabout 2° C. above the transition temperature (i.e., where T-5° C. 5 mpT+2° C.), where T is the transition temperature.

In various aspects, the high-temperature thermal pellet compositionscomprise organic compounds or materials that are selected to meet one ormore of the following criterion. In certain aspects, the organiccompositions selected for use in the high-temperature thermal pellethave a relatively high chemical purity. For example, in certainembodiments, desirable chemical candidates for the high temperaturethermal pellet compositions have a range of purity levels from about 95%up to 99+%. In certain aspects, the organic compositions selected foruse in the high temperature thermal pellets are particularly suitablefor processing, handling, and toxicity characteristics. In certainembodiments, the organic chemical compounds or compositions selected foruse in the high-temperature pellet compositions have a median lethaldose toxicity value (LD₅₀) less than or equal to about 220 mg/kg (ppm)for a mouse; less than or equal to about 400 mg/kg (ppm) for a rabbit;and less than or equal to about 350 mg/kg (ppm) for a rat. Further, incertain aspects, the selected organic chemical compositions for thehigh-temperature thermal pellet desirably do not have documentedcarcinogenicity effects, mutagenicity effects, neurotoxicity effects,reproductive effects, teratogenicity effects, and/or other harmfulhealth or epidemiological effects. In yet other aspects, the organiccomponents for the high temperature thermal pellet compositions areselected such that alternate reactive residuals, reaction productsformed during manufacture, decomposition products, or other species thatmight be formed during manufacture, storage, or use are absent,minimized, or are capable of purification and removal of such undesiredspecies.

In certain aspects, the compositions selected for use in the hightemperature thermal pellet composition exhibit long-term stability. Byway of example, compositions are optionally selected to possesstemperature or thermal stability, in other words, chemical compoundsthat show decomposition or volatility behavior within about 10° C.,optionally within about 20° C., optionally within about 30° C.,optionally within about 40° C., optionally within about 50° C.,optionally within about 60° C., optionally within about 75° C., and incertain aspects, optionally within about 100° C. of the transitiontemperature or melting point of the organic compound may be rejected asviable candidates. Further, in certain embodiments, chemicalcompositions suitable for use as high-temperature thermal pelletcompositions will not show a strong likelihood of heat-induced andage-progressive oxidation or decomposition.

Further, suitable compositions for high-temperature thermal pelletsinclude those that are “electrically non-conductive,” meaning that thecomposition is capable of withstanding a 240 volt, 60 Hz sinusoidalpotential between two electrodes at least about 5° C. above the T_(f)final temperature for at least one minute without conducting greaterthan 250 mA. In certain aspects, the select composition should becapable of withstanding a 240 volt, 60 Hz sinusoidal potential at least10° C. above the T_(f) final temperature for at least about one minutewithout conducting greater than 250 mA. In yet other aspects, thehigh-temperature thermal cutoff compositions are optionally capable ofwithstanding a 240 volt, 60 Hz sinusoidal potential at least 50° C.above the final transition temperature T_(f) for at least about oneminute without conducting greater than 250 mA of current.

In various aspects, the organic chemical compositions that are selectedfor use in the high temperature thermal composition have an initialmelting point temperature of at least about 240° C., optionally about241° C., optionally about 242° C., optionally about 243° C., optionallyabout 244° C., optionally about 245° C., optionally about 246° C.,optionally about 247° C., optionally about 248° C., optionally about249° C., optionally about 250° C., optionally about 251° C., optionallyabout 252° C., optionally about 253° C., optionally about 254° C.,optionally about 255° C., optionally about 256° C., optionally about257° C., optionally about 258° C., optionally about 259° C., optionallyabout 260° C., optionally about 261° C., optionally about 262° C.,optionally about 263° C., optionally about 264° C., optionally about265° C., optionally about 266° C., optionally about 267° C., optionallyabout 268° C., optionally about 269° C., optionally about 270° C.,optionally about 271° C., optionally about 272° C., optionally about273° C., optionally about 274° C., optionally about 275° C., optionallyabout 276° C., optionally about 277° C., optionally about 278° C.,optionally about 279° C., optionally about 280° C., optionally about281° C., optionally about 282° C., optionally about 283° C., optionallyabout 284° C., optionally about 285° C., optionally about 286° C.,optionally about 287° C., optionally about 288° C., optionally about289° C., optionally about 290° C., optionally about 291° C., optionallyabout 292° C., optionally about 293° C., optionally about 294° C.,optionally about 295° C., optionally about 296° C., optionally about297° C., optionally about 298° C., optionally about 299° C., optionallyabout 300° C., and in certain embodiments, optionally about 301° C. Incertain aspects, the melting point of the organic composition for thehigh-temperature thermal pellet is greater than 275° C. and in certainaspects, optionally greater than 300° C. In certain embodiments, organiccompounds that meet the above selection criteria and that can remain asolid at temperatures ranging from 50° C. to at least 235° C. aredesirable. In certain aspects, organic compounds that can remain astable solid up to about 236° C., optionally up to about 237° C.,optionally up to about 238° C., optionally up to about 239° C.,optionally up to about 240° C., optionally up to about 245° C.,optionally up to about 250° C., optionally up to about 255° C.,optionally up to about 260° C., optionally up to about 265° C.,optionally up to about 270° C., optionally up to about 275° C.,optionally up to about 280° C., optionally up to about 285° C.,optionally up to about 290° C., optionally up to about 295° C., and incertain aspects, optionally up to or exceeding about 300° C.

Suitable organic compound candidates for the high-temperature thermalpellets of the HTTCO devices of the present disclosure optionallyinclude the following additional characteristics. In certainembodiments, organic chemicals having acidic structures, such asstructures with multiple hydroxides or structures which might have ionicactivity in an electrical field may be avoided or minimized. Further,certain organic compounds having side groups comprising sulfur can beavoided, as are compounds having bond structures that easily break downin an electrical field in certain applications.

In certain embodiments, the selection of organic compounds useful as athermal cutoff composition herein can be made based on the chemical'sbehavior in relation to and interaction with the seal material for thehousing of the HTTCO, which often is a porous polymeric structure.Suitable organic chemical compounds for the high-temperature thermalpellet include those having a relatively large molecular size, forexample, organic molecules having ring structures, such as those thatoccupy dimensional space due to bending or side groups. In certainaspects, suitable chemical candidates having flat or unbentconformations or chemical structures, which may have shear mobility or arelatively unimpaired navigation path through the pores in the sealmaterial, are avoided. As such, in certain aspects, the organic chemicalcompounds selected for use in the high-temperature thermal pelletcompositions have relative molecular complexity, such as organicpolycyclic ring structures with complex bond orientations that createirregular dimensional space filling configurations or conformations. Forexample, certain chemical structures that “tangle” at high energy statesare desirable, as are relatively large organic species having complexside chains.

Furthermore, suitable chemical compounds for the high-temperaturethermal compositions of the present disclosure include those that havehigh molecular bond strength, for example, in ring structures likepolyaromatic, polyalkyl, heteroalkyl rings, including fused ringstructures that share one or more common bonds. Chemical structureshaving high intrabond strength with other rings or side groups are alsosuitable organic species. Further, chemical compounds havingintermolecular bond strength, including non-polar or relatively lowpolar strength structures with high instantaneous polarizability arealso suitable. For example, structures with side groups that have “bondaffinities” for the parent ring or side groups of other molecular groupsare desirable.

High melting point aromatic compounds have been shown to provide uniquebond strength, relatively large molecule size and electronegativitycharacteristics desirable to perform as high-temperature thermal cutofforganic compounds when formulated into solid shapes such as pellets andthe like. In certain embodiments, the thermal cutoff composition caninclude one or more aromatic compounds, one or more five-membered ringcompounds, polymers, co-polymers, and mixtures thereof.

In certain aspects, the high-temperature thermal pellets may comprise aplurality of organic compounds as primary components. Thus, thehigh-temperature pellet compositions for the HTTCO devices of thepresent disclosure optionally comprise one or more organic compoundsthat will provide a transition temperature of greater than or equal toabout 240° C. In certain aspects, a plurality of such organiccompositions can be used, such that the resulting melting point of themixture provides the predetermined desired transition temperature forthe pellet composition. As recognized by those of skill in the art, thecombination of various organic compositions or other components willresult in a thermal pellet transition temperature T_(x) expressed by thefollowing relationship of.

${{\sum\limits_{n}^{1}{X_{n} \times {{mp}_{n}\left( {{^\circ}\mspace{14mu} {C.}} \right)}}} = T_{x}},$

where X_(n) is the mass fraction of each respective component present inthe pellet composition (where n is greater than 1) and “mp_(n)” is theinitial melting point temperature for each respective component. In thismanner, a transition temperature of the thermal pellet can be predictedbased on the respective melting points of a plurality of organiccompounds present in the thermal pellet composition. In certain aspects,the pellet composition may comprise a single organic composition as theprimary ingredient to arrive at a T_(x) of greater than or equal toabout 240° C. In other aspects, the pellet composition may comprise aplurality of organic compositions, for example two or more organiccompounds, to arrive at a T_(x) of greater than or equal to about 240°C. Such organic compounds may have different melting point temperaturesor other properties and are can be combined by co-precipitation,co-crystallization, mixing, blending, milling, or otherwise combined ina suitable manner known in the art.

In some embodiments, a high-temperature thermal pellet compositioncomprises one or more compounds, which includes compounds with achemical structure having one or more six-member rings that has a basicbackbone of carbon with side constituent groups that may be the same ordifferent. In some embodiments, the thermal cutoff composition caninclude one or more chemical entities generally described by astructural repeating unit (SRU): (-PhRR′-)_(n) where R and R′ may be thesame or different side constituent groups, and wherein n may also be avalue or greater than or equal to 1, designating the repetition of thestructure repeating unit (SRU). In some embodiments, the hightemperature thermal pellet composition can include one or more 5 memberring structures, where the side groups and/or SRU may have may be thesame or different entities (e.g., having different side constituentgroups) such as, for example, where the thermal cutoff composition isdescribed as an example, by the nominal SRU formula,(-Ph-RR¹)_(n)-(-Ph-R²R³)_(m), wherein R and R¹ are distinct side groupsfrom R² and R³. In some embodiments, R and R¹ may be the same ordifferent, and similarly, R² and R³ may be the same or different.

In some embodiments, the term “hydrocarbyl” is used herein to refergenerally to organic groups comprised of carbon chains to which hydrogenand optionally other elements are attached. CH₂ or CH groups and C atomsof the carbon chains of the hydrocarbyl may be replaced with one or moreheteroatoms (i.e., non-carbon atoms). Suitable heteroatoms include butare not limited to O, S, P and N atoms. Illustrative hydrocarbyl groupscan include, but are not limited to alkyl, alkenyl, alkynyl, ether,polyether, thioether, straight chain or cyclic saccharides, ascorbate,aminoalkyl, hydroxylalkyl, thioalkyl, aryl and heterocyclic aryl groups,optionally substituted tricyclic molecules, amino acid, polyalcohol,glycol, groups which have a mixture of saturated and unsaturated bonds,carbocyclic rings and combinations of such groups. The term alsoincludes straight-chain, branched-chain and cyclic structures orcombinations thereof. Hydrocarbyl groups are optionally substituted.Hydrocarbyl substitution includes substitution at one or more carbons inthe group by moieties containing heteroatoms.

Suitable substituents for hydrocarbyl groups include but are not limitedto halogens, including chlorine, fluorine, bromine and iodine, OH, SH,—N—OH, NH, NH₂, —C—NH₂═S, CH, —CH—O, C═N, —C—N═O, —C—NH₂═O, C═O, COH,—C—NH₂═S, CO₂, H, —CHBN, —CHP, OR¹, SR¹NR¹, R″, CONR¹R², andcombinations thereof, where R¹ and R² independently are alkyl,unsaturated alkyl or aryl groups. The term “alkyl” takes its usualmeaning in the art and is intended to include straight-chain, branchedand cycloalkyl groups. The term includes, but is not limited to, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,n-pentyl, neopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl,1,1-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl,1,1-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl,n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl,1-methylhexyl, 3-ethylpentyl, 2-ethylpentyl, 1-ethylpentyl,4,4-dimethylpentyl, 3,3-dimethylpentyl, 2,2-dimethylpentyl,1,1-dimethylpentyl, n-octyl, 6-methylheptyl, 5-methylheptyl,4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl,1-ethylhexyl, 1-propylpentyl, 3-ethylhexyl, 5,5-dimethylhexyl,4,4-dimethylhexyl, 2,2-diethylbutyl, 3,3-diethylbutyl, and1-methyl-1-propylbutyl. Alkyl groups are optionally substituted. Loweralkyl groups are C₁-C₆ alkyl and include among others methyl, ethyl,n-propyl, and isopropyl groups.

The term “cycloalkyl” refers to alkyl groups having a hydrocarbon ring,particularly to those having rings of 3 to 7 carbon atoms. Cycloalkylgroups include those with alkyl group substitution on the ring.Cycloalkyl groups can include straight-chain and branched-chainportions. Cycloalkyl groups include but are not limited to cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, andcyclononyl. Cycloalkyl groups can optionally be substituted.

Aryl groups may be substituted with one, two or more simple substituentsincluding, but not limited to, lower alkyl, e.g., C₁-C₄, methyl, ethyl,propyl, butyl; halo, e.g., chloro, bromo; nitro; sulfato; sulfonyloxy;carboxy; carbo-lower-alkoxy, e.g., carbomethoxy, carbethoxy; amino;mono- and di-lower-alkylamino, e.g., methylamino, ethylamino,dimethylamino, methylethylamino; amido; hydroxy; lower-alkoxy, e.g.,methoxy, ethoxy; and lower-alkanoyloxy, e.g., acetoxy.

The term “unsaturated alkyl” group is used herein generally to includealkyl groups in which one or more single carbon-carbon bonds are doubleor triple carbon-carbon bonds. The term includes alkenyl and alkynylgroups in their most general sense. The term is intended to includegroups having more than one double or triple bond, or combinations ofdouble and triple bonds. Unsaturated alkyl groups include, withoutlimitation, unsaturated straight-chain, branched or cycloalkyl groups.Unsaturated alkyl groups include without limitation: vinyl, allyl,propenyl, isopropenyl, butenyl, pentenyl, hexenyl, hexadienyl, heptenyl,cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl,cyclohexenyl, cyclohexadienyl, 1-propenyl, 2-butenyl,2-methyl-2-butenyl, ethynyl, propynyl, 3-methyl-1-pentynyl, and2-heptynyl. Unsaturated alkyl groups can optionally be substituted.

Substitution of alkyl, cycloalkyl and unsaturated alkyl groups includessubstitution at one or more carbons in the group by moieties containingheteroatoms. Suitable substituents for these groups include but are notlimited to OH, SH, NH₂, COH, CO₂H, OR³, SR³, P, PO, NR³R⁴, CONR³R⁴, andhalogens, particularly chlorines and bromines where R³ and R⁴,independently are alkyl, unsaturated alkyl or aryl groups. Suitablealkyl and unsaturated alkyl groups are the lower alkyl, alkenyl oralkynyl groups having from 1 to about 5 carbon atoms.

The term “aryl” is used herein generally to refer to aromatic groupswhich have at least one ring having a conjugated pi electron system andincludes without limitation carbocyclic aryl, aralkyl, heterocyclicaryl, biaryl groups and heterocyclic biaryl, all of which can beoptionally substituted. Preferred aryl groups have one or two aromaticrings. “Carbocyclic aryl” refers to aryl groups in which the aromaticring atoms are all carbons and includes without limitation phenyl,biphenyl and napthalene groups.

“Aralkyl” refers to an alkyl group substituted with an aryl group.Suitable aralkyl groups include among others benzyl, phenethyl, and maybe optionally substituted, such as picolyl substituted with nitrogen.Aralkyl groups include those with heterocyclic and carbocyclic aromaticmoieties.

“Heterocyclic aryl groups” refers to groups having at least oneheterocyclic aromatic ring with from 1 to 3 heteroatoms in the ring, theremainder being carbon and hydrogen atoms. Suitable heteroatoms includewithout limitation oxygen, sulfur, and nitrogen. Heterocyclic arylgroups include among others furanyl, thienyl, pyridyl, pyrrolyl, N-alkylpyrrolo, pyrimidyl, pyrazinyl, imidazolyl, benzofuranyl, quinolinyl, andindolyl, all optionally substituted.

“Heterocyclic biaryl” refers to heterocyclic aryls in which a phenylgroup is substituted by a heterocyclic aryl group ortho, meta or para tothe point of attachment of the phenyl ring to the decalin orcyclohexane. Heterocyclic biaryl includes among others groups which havea phenyl group substituted with a heterocyclic aromatic ring. Thearomatic rings in the heterocyclic biaryl group can be optionallysubstituted.

“Biaryl” refers to carbocyclic aryl groups in which a phenyl group issubstituted by a carbocyclic aryl group ortho, meta or para to the pointof attachment of the phenyl ring to the decalin or cyclohexane. Biarylgroups include among others a first phenyl group substituted with asecond phenyl ring ortho, meta or para to the point of attachment of thefirst phenyl ring to the decalin or cyclohexane structure. Parasubstitution is preferred. The aromatic rings in the biaryl group can beoptionally substituted.

Aryl group substitution includes substitutions by non-aryl groups(excluding H) at one or more carbons or where possible at one or moreheteroatoms in aromatic rings in the aryl group. Unsubstituted aryl, incontrast, refers to aryl groups in which the aromatic ring carbons areall substituted with H, e.g. unsubstituted phenyl (—C₆H₅), or naphthyl(—C₁₀H₇). Suitable substituents for aryl groups include among others,alkyl groups, unsaturated alkyl groups, halogens, OH, SH, NH₂, COH,CO₂H, OR⁵, SR⁵, NR⁵, R⁶, CONR⁵, R⁶, where R⁵ and R⁶ independently arealkyl, unsaturated alkyl or aryl groups. Preferred substituents are OH,SH, OR⁵, and SR⁵ where R⁵ is a lower alkyl, i.e., an alkyl group havingfrom 1 to about 5 carbon atoms. Other preferred substituents arehalogens, more preferably chlorine or bromine, and lower alkyl andunsaturated lower alkyl groups having from 1 to about 5 carbon atoms.Substituents include bridging groups between aromatic rings in the arylgroup, such as —CO₂—, —CO—, —NH—, —CH═CH—and —(CH₂)_(I)— where I is aninteger from 1 to about 5, and particularly —CH₂— where I is 1. Examplesof aryl groups having bridging substituents include phenylbenzoate.Substituents also include moieties, such as —(CH₂)_(J)—, —O—(CH₂)_(J)—or —OCO—(CH₂)_(J)—, where J is an integer from about 2 to 7, asappropriate for the moiety, which bridge two ring atoms in a singlearomatic ring as, for example, in a 1,2,3,4-tetrahydronaphthalene group.Alkyl and unsaturated alkyl substituents of aryl groups can in turnoptionally be substituted as described supra for substituted alkyl andunsaturated alkyl groups.

The terms “alkoxy group” and “thioalkoxy group” (also known asmercaptide groups, the sulfur analog of alkoxy groups) take theirgenerally accepted meaning. Alkoxy groups include but are not limited tomethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy,tert-butoxy, n-pentyloxy, neopentyloxy, 2-methylbutoxy, 1-methylbutoxy,1-ethyl propoxy, 1,1-dimethylpropoxy, n-hexyloxy, 1-methylpentyloxy,2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy,3,3-dimethylbutoxy, 2,2-dimethoxybutoxy, 1-1-dimethylbutoxy,2-ethylbutoxy, 1-ethylbutoxy, 1,3-dimethylbutoxy, n-pentyloxy,5-methylhexyloxy, 4-methylhexyloxy, 3-methylhexyloxy, 2-methylhexyloxy,1-methylhexyloxy, 3-ethylpentyloxy, 2-ethylpentyloxy, 1-ethylpentyloxy,4,4-dimethylpentyloxy, 3,3-dimethylpentyloxy, 2,2-dimethylpentyloxy,1,1-dimethylpentyloxy, n-octyloxy, 6-methylheptyloxy, 5-methylheptyloxy,4-methylheptyloxy, 3-methylheptyloxy, 2-methylheptyloxy,1-methylheptyloxy, 1-ethylhexyloxy, 1-propylpentyloxy, 3-ethylhexyloxy,5,5-dimethylhexyloxy, 4,4-dimethylhexyloxy, 2,2-diethylbutoxy,3,3-diethylbutoxy, 1-methyl-1-propylbutoxy, ethoxymethyl,n-propoxymethyl, isopropoxymethyl, sec-butoxymethyl, isobutoxymethyl,(1-ethyl propoxy)methyl, (2-ethylbutoxy)methyl, (1-ethylbutoxy)methyl,(2-ethylpentyloxy)methyl, (3-ethylpentyloxy)methyl, 2-methoxyethyl,1-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 2-methoxypropyl,1-methoxypropyl, 2-ethoxypropyl, 3-(n-propoxy)propyl, 4-methoxybutyl,2-methoxybutyl, 4-ethoxybutyl, 2-ethoxybutyl, 5-ethoxypentyl, and6-ethoxyhexyl. Thioalkoxy groups include but are not limited to thesulfur analogs of the alkoxy groups specifically listed supra.

In some embodiments, the R, R¹, R², R³, R⁴, R⁵ and R⁶ side groups in the5 and 6 member ring can be independently selected from any of theaforementioned hydrocarbyl substituents, for example, —CH, —CH—O,—CH—OH, —NH₂, —NH, —CH—N, —CH═O, —N—OH, —CHBN, —CHP or mixtures thereof.

In certain aspects, one particularly suitable organic compounds for usein a high-temperature thermal pellet composition of the presentteachings is triptycene or tryptycene(9,10-dihydro-9,10-o-benzeno-9,10-dihydroanthracene—CAS Registry No.477-75-8), which has a transition temperature of about 255° C. and amelting point temperature range of 255° C. to about 257° C. Triptyceneis generally classified as a polycyclic aromatic hydrocarbon and isgenerally represented by the exemplary Formula (I):

Triptycene can be prepared by the reduction of theanthracene-benzoquinone adduct with lithium aluminum hydride or sodiumborohydride, among other methods known to those in the art. Tryptycene,or triptycene (also known as) is described in Organic Syntheses, Coll.Vol. 4, p. 964 (1963), the relevant portions of which are incorporatedherein by reference.

In certain other aspects, a particularly suitable organic compound foruse in a high-temperature thermal pellet composition of the presentteachings is 1-aminoanthraquinone (also known as1-Amino-9,10-anthracenedione—CAS Registry No. 82-45-1), which isclassified as a polycyclic aromatic hydrocarbon with constituent sidegroups —C═O and C—NH₂ as represented in Formula (II):

1-Aminoanthraquinone has an expected transition temperature of about253° C., with a melting point range of 253° C. to about 257° C.1-Aminoanthraquinone (1-AAQ) can be prepared by the reaction of2-chlorobenzyl chloride and xylene in the presence of a solid acidcatalyst, or other methods known in the art. 1-aminoanthraquinone (alsoknown as 1-Amino-9,10-anthracenedione) described in U.S. Pat. Nos.4,006,170 and 4,695,407, the relevant portions of which are incorporatedherein by reference.

By way of non-limiting example, other representative organic compounds,such as the exemplary compounds set forth in Table 2 below are alsobelieved to be highly suitable candidates for the high-temperaturethermal pellet compositions for the HTTCO devices of the presentdisclosure, based on the criteria discussed above and the estimatedmelting point temperature ranges set forth below. However, the presentdisclosure further contemplates various other organic compounds, whichwhile not listed herein, fulfill one or more of the criteria listedabove including the melting point data that corresponds to a transitiontemperature above about 240° C. As noted above, predicted melting pointranges may differ based on analytic techniques used (thus certaincompounds have multiple or differing melting points) and suchcompositions are selected to have an empirical transition temperaturethat performs in a thermal pellet to physically transition and changeelectrical continuity at a desired threshold temperature.

TABLE 2 Example Melting Point Name IUPAC Name CAS Registry No. 1 241° C.Zaprinast 5-(2-propoxyphenyl)-2,3- 37762-06-4dihydrotriazolo[4,5-e]pyrimidin- 7-one 2 241-243° C. Ropinirolehydrochloride 4-[2-(dipropylamino)ethyl]-1,3- 91374-20-8dihydroindol-2-one hydrochloride 3 241° C. Triphenylguanidine(N,N′-diphenylcarbamimidoyl)- 59283-92-0 hydrochloride phenylazaniumchloride 4 241-242° C. Naphthacene, 1,4,5,6,7,10,11,12- 60700-47-21,4,5,6,7,10,11,12-octahydro- octahydrotetracene 5 241-244° C.3-Ethoxybenzonitrile 3-ethoxybenzonitrile 25117-75-3 6 241-242° C.Cis-1,2,3,4-Tetrahydro-1- (1S,4S)-N-methyl-4-phenyl- 52371-38-7amino-N-methyl-4- 1,2,3,4-tetrahydronaphthalen- phenylnaphthalene1-amine hydrochloride hydrochloride 7 241° C. 2,7-Dimethylanthracene2,7-dimethylanthracene 782-23-0 8 240-243° C. Sesbanine3′-hydroxyspiro[2,7- 70521-94-7 naphthyridine-4,1′-cyclopentane]-1,3-dione 9 241-243° C. 1,3,4-Oxadiazole, 2-amino-5-5-phenyl-1,3,4-oxadiazol-2- 1612-76-6 phenyl- amine 10 241° C.Acenaphtho(1,2- acenaphthyleno[1,2- 207-11-4 b]quinoxaline b)quinoxaline11 242° C. Oxyphenisatin [4-[3-(4-acetyloxyphenyl)-2- 115-33-3 Acetateoxo-1H-indol-3-yl]phenyl] acteate 12 242° C. 4-Nitrobenzimidazole4-nitro-1H-benzimidazole 10597-52-1 13 242-244° C. Biotinamide5-[(3aR,6S,6aS)-2-oxo- 6929-42-6 1,3,3a,4,6,6a- hexahydrothieno[3,4-d]imidazol-6-yl]pentanamide 14 242° C. Tropine isobutyrate[(1S,5R)-8-methyl-8- 495-80-7 azabicyclo[3.2.1]octan-3-yl] 2-methylpropanoate 15 242° C. Phenol, 2-(1H-benzimidazol-6-(1,3-dihydrobenzimidazol-2- 2963-66-8 2-yl)-ylidene)cyclohexa-2,4-dien-1- one 16 242-245° C. Bufalone 5- 4029-65-6[(5R,8R,9S,10S,13R,14S,17R)- 14-hydroxy-10,13-dimethyl-3- oxo-2,4,5,6,7,8,9,11,12,15,16,17- dodecahydro-1H-cyclopenta[a]phenanthren-17- yl]pyran-2-one 17 242-244° C. Difenoximidehydrochloride (2,5-dioxopyrrolidin-1-yl) 1-(3- 37800-79-6cyano-3,3-diphenylpropyl)-4- phenylpiperidine-4-carboxylatehydrochloride 18 242-244° C. Levcromakalim (3S,4R)-3-hydroxy-2,2-94535-50-9 dimethyl-4-(2-oxopyrrolidin-1- yl)chroman-6-carbonitrile 19242-243° C. Bandrowski's base 3,6-bis[(4- 20048-27-5aminophenyl)imino]cyclohexa- 1,4-diene-1,4-diamine 20 242° C.pyrazino[2,3-f] quinoxaline pyrazino[2,3-f]quinoxaline 231-23-2 21243-245° C. 2,4,6-Tri-2-pyridinyl-1,3,5- 2,4,6-tri(pyridin-2-yl)-1,3,5-3682-35-7 triazine triazine 22 243-245° C.3,3′,5,5′-Tetra-tert-butyl[di- 2,6-ditert-butyl-4-(3,5-ditert- 2455-14-32,5-cyclohexadien-1-ylidene]- butyl-4-oxo-1-cyclohexa-2,5- 4,4′-dionedienylidene)cyclohexa-2,5- dien-1-one 23 243-245° C. 6-Methyl-8-6-methyl-8-nitrophenanthridine 51381-78-3 nitrophenanthridine 24243-245° C. 1,4-Dihydro-5H-tetrazol-5-one 1,2-dihydrotetrazol-5-one16421-52-6 25 242.5-243° C. 2,2′-Diamino-1,1′-binaphthyl1-(2-aminonaphthalen-1- 18741-85-0 yl)naphthalen-2-amine 26 243° C.Violerythrin 3,5,5-trimethyl-4- 22453-06-1 (236-238°)[(1E,3E,5E,7E,9E,11E,13E,15E,17E)- 3,7,12,16-tetramethyl-18-(2,5,5-trimethyl-3,4-dioxo- 1-cyclopentenyl)octadeca-1,3,5,7,9,11,13,15,17- nonaenyl]cyclopent-3-ene-1,2- dione 27 243-245°C. Acenapththenequinone acenaphthene-1,2-dione 82-86-0 28 243° C. Durylaldehyde 2,4,5-trimethylbenzaldehyde 5779-72-6 29 244-245.5° C.Longimammatine 6-methoxy-1,2,3,4- 42923-77-3 tetrahydroisoquinoline 30244-245° C. Proguanil Hydrochloride (1Z)-1-[amino-[(4- 637-32-1chlorophenyl)amino]methylidene]- 2-propan-2-ylguanidine hydrochloride 31244-247° C. 2H-1-Benzopyran-2-one, 5- 5-hydroxychromen-2-one 6093-67-0hydroxy- 32 244-245° C.; N,N′-Diphenylbenzidine N-phenyl-4-[4- 531-91-9251-252° C. (phenylamino)phenyl]aniline 33 244-245° C. Methanone,bis(4-aminophenyl)methanone 611-98-3 bis(4-aminophenyl)- 34 244° C.Dapitant (2S)-1-[(3aS,4S,7aS)-4- 153438-49-4hydroxy-4-(2-methoxyphenyl)- 7,7-di(phenyl)-1,3,3a,5,6,7a-hexahydroisoindol-2-yl]-2-(2- methoxyphenyl)propan-1-one 35 244-245° C.Cytosinine 3-amino-6-(4-amino-2- 1860-84-0oxopyrimidin-1-yl)-3,6-dihydro- 2H-pyran-2-carboxylic acid 36 244-245°C. Biurea (carbamoylamino)urea 110-21-4 37 244-245° C. 9,10-anthracene-9,10- 7044-91-9 Anthracenedicarboxaldehyde dicarbaldehyde 38244-246° C. Tri-3-indolylmethane 3-[bis(1H-indol-3-yl)methyl]- 518-06-91H-indole 39 245° C. 6-Benzyl-1,3,5-triazine-2,4-6-(phenylmethyl)-1,3,5- 1853-88-9 diamine triazine-2,4-diamine 40 245°C. Taraxerone (4aR,6aR,6aS,8aR,12aS,14aR,14bR)- 514-07-84,4,6a,6a,8a,11,11,14b- octamethyl- 2,4a,5,6,8,9,10,12,12a,13,14,14a-dodecahydro-1H-picen-3-one 41 245-246° C. 1,7-Dihydro-1,7-dimethyl-6H-1,7-dimethylpurin-6-one 33155-83-8 purin-6-one 42 245-246° C.1-Phenazinecarboxamide phenazine-1-carboxamide 550-89-0 43 245° C.Methisazone [(1-methyl-2-oxoindol-3- 1910-68-5 ylidene)amino]thiourea 44245-247° C. 3-Indazolinone 1,2-dihydroindazol-3-one 7364-25-2 45245-246° C. Emd 56431 (3R,4S)-3-hydroxy-2,2- 123595-75-5dimethyl-4-(2-oxopyridin-1- yl)chroman-6-carbonitrile 46 245-246.5° C.Dimoxamine hydrochloride 1-(2,5-dimethoxy-4- 52663-86-2methylphenyl)butan-2-amine hydrochloride 47 245-247° C.9H-Carbazol-2-amine (9Cl) 9H-carbazol-2-amine 4539-51-9 48 245-247° C.(1,2,4)Triazolo(4,3-a)pyridin- [1,2,4]triazolo[4,5-a]pyridin-3- 767-62-43(2H)-imine amine 49 246-248° C. Carbanilide 1,3-di(phenyl)urea 102-07-8(239-240° C.) 50 246-247° C. 1H-1,2,3-Triazlo(4,5-2H-triazolo[4,5-c]pyridine 273-05-2 c)pyridine 51 246-248° C.Hexamethylbenzene- [4-(hydroxymethyl)-2,3,5,6- 7522-62-5alpha1,alpha4-diol tetramethylphenyl]methanol 52 246-247° C.6-Thiocaffeine 1,3,7-trimethyl-6- 13182-58-6 sulfanylidenepurin-2-one 53246-249° C. 1,2,3,4-Tetrahydro-9H- 1,2,3,4-tetrahydrocarbazole-9-67242-61-9 carbazole-9-carboxamide carboxamide 54 246-248° C.9,10-Diphenylanthracene 9,10-di(phenyl)anthracene 1499-10-1 55 246° C. O129 6,7-di(propan-2-yl)pteridine- 3810-29-5 2,4-diamine 56 246° C.9,9′-Bi-9H-fluorene 9-(9H-fluoren-9-yl)-9H-fluorene 1530-12-7 57246-248° C. 2-[4- 2-[4- 18643-56-6(dicyanomethyl)phenyl]propanedinitrile(dicyanomethyl)phenyl]propanedinitrile 58 247-248° C. Sulfaquinoxaline4-amino-N-quinoxalin-2- 59-40-5 ylbenzenesulfonamide 59 247° C.Metaldehyde 2,4,6,8-tetramethyl-1,3,5,7- 108-62-3 tetraoxocane 60247-250° C. 1-Azaspiro(5.5)undecan-8-ol, 7-[(E)-but-1-en-3-ynyl]-2-pent-63983-63-1 7-(1-buten-3-ynyl)-2-(4- 4-ynyl-1- pentynyl)-, (6R-azaspiro[5.5]undecan-8-ol (6alpha(R*),7beta(Z),8alpha))- 61 247-249° C.9H-Pyrido(3,4-b)indole-3- N-ethyl-9H-pyrido[5,4-b]indole- 78538-80-4carboxamide, N-ethyl- 3-carboxamide 62 247-248° C. Apazone5-dimethylamino-9-methyl-2- 13539-59-8 propylpyrazolo[1,2-a][1,2,4]benzotriazine-1,3- dione 63 247-251° C.4,4′,5,5′-Tetraphenyl-Δ^(2,2′)-bi- N-[(4- 14551-06-5 2H-imidazolecarbamimidoylphenyl)methyl]- 2-[5-chloro-3-(3-hydroxypropylamino)-2-oxo-6- phenylpyrazin-1-yl]acetamide 64 247° C.2-Hydroxy-3- 3-phenyl-1H-quinoxalin-2-one 1504-78-5 phenylquinoxaline 65247-249° C. 3-Hydroxy-19-norpregna- 1-[(8S,9S,13S,14S,17S)-3- 1667-98-71,3,5(10)-trien-20-one hydroxy-13-methyl- 6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren- 17-yl]ethanone 66 248° C. CP 931293-(1,2,3,6-tetrahydropyridin-4- 127792-75-0 yl)-1,4-dihydropyrrolo[2,3-e]pyridin-5-one 67 248° C. 6-Benzyl-1,3,5-triazine-2,4-6-(phenylmethyl)-1,3,5- 1853-88-9 (238-299°) diaminetriazine-2,4-diamine 68 248-250° C. 6-Hydroxychrysene chrysen-6-ol37515-51-8 69 248° C. Tetraphenylpyrazine 2,3,5,6-tetra(phenyl)pyrazine642-04-6 70 249-251° C. 2,4,6-Pyrimidinetriaminepyrimidine-2,4,6-triamine 1004-38-2 71 249° C.Pyrazino[2,3-b]quinoxaline pyrazino[2,3-b]quinoxaline 261-67-6 72249-250° C. 6-Hydrazino-3- 6-hydrazinylpyridazine-3- 3614-47-9pyridazinecarboxamide carboxamide 73 249° C. 4-NitrophenylhydrazoneN-[(2- 14295-17-1 chlorophenyl)methylideneamino]- 4-nitroaniline 74249-253° C. N¹,N⁴-Di-E- 3-phenyl-N-[4-(3-phenylprop- 37946-56-8cinnamoylputrescine 2-enoylamino)butyl]prop-2- enamide 75 249-250° C.1-Aminothioxanthen-9-one 1-aminothioxanthen-9-one 40021-31-6 76 249-250°C. 1-Naphthylamine, 5-methoxy- (5-methoxy-1,2,3,4- 41566-70-51,2,3,4-tetrahydro- tetrahydronaphthalen-1- hydrochloride yl)azaniumchloride 77 250° C. NCS404824 7H-[1,2,4]triazolo[5,1-f]purine 4022-94-078 250-252° C. 2,4-Quinazolinediamine quinazoline-2,4-diamine 1899-48-579 250° C. Prioxodan 3-methyl-6-(6-oxo-4,5-dihydro- 111786-07-31H-pyridazin-3-yl)-1,4- dihydroquinazolin-2-one 80 250° C.2,6-dimethylanthracene 2,6-dimethylanthracene 613-26-3 81 250° C.4,4′-Diaminoazobenzene 4-(4- 538-41-0 aminophenyl)diazenylaniline 82250-253° C. N,N-Dimethyl-4-t-butylaniline 4-tert-butyl-N,N- 2909-79-7dimethylaniline 83 250-251° C. Acetamide N-chrysen-5-ylacetamide34441-00-4 84 230°; 250° C. 1-Acridinol 10H-acridin-1-one 5464-73-3 85251-252° C. 2-Phenyl-1H-indole-3- 2-phenyl-1H-indole-3- 25365-71-3carboxaldehyde carbaldehyde 86 251° C. Fluorene-9-carboxamide9H-fluorene-9-carboxamide 7471-95-6 87 251-253° C. 2,3-Dimethylcarbazole2,3-dimethyl-9H-carbazole 18992-70-6 88 251-253° C. 9,10-bis(2-9,10-bis(2- 10075-85-1 phenylethynyl)anthracene phenylethynyl)anthracene89 251-253° C. 6-Dimethyladenine N,N-dimethyl-7H-purin-6- 938-55-6 amine90 252-254° C. 6-Quixoxalinol 4H-quinoxalin-6-one 7467-91-6 91 252-254°C. Oxalanilide N,N′-di(phenyl)oxamide 620-81-5 92 252-255° C.3-(Hydroxyimino)-7- 3-(hydroxyamino)-7- 13208-96-3 methylindolin-2-onemethylindol-2-one 93 252° C. 2,3-Dimethylanthracene2,3-dimethylanthracene 613-06-9 94 252-255° C.2,4-Dinitrophenylhydrazone 2,4-dinitro-N-[(2- 16281-65-5phenylchroman-4- ylidene)amino]aniline 95 252-252.5° C.Cyclopent(b)indol-3-one, 2,4-dihydro-1H- 16244-15-8 1,2,3,4-tetrahydro-cyclopenta[b]indol-3-one 96 253-254° C. 1-Aminoanhraquinone1-aminoanthracene-9,10-dione 82-45-1 97 253° C. 2-Benzothiazolamine,6-nitro- 6-nitro-1,3-benzothiazol-2- 6285-57-0 amine 98 253° C.2H-1,3-Benzoxazine-2,4(3H)- 2-sulfanylidene-1,3- 10021-35-9 dione,2-thio- benzoxazin-4-one 99 254-255° C. 7H-Pyrido(3,4-c)carbazole7H-pyrido[3,4-c]carbazole 205-27-6 100 254-255° C. Tetrahydroharmol1-methyl-2,3,4,9-tetrahydro- 17952-75-9 hydrochloride1H-pyrido[3,4-b]indol-7-ol hydrochloride 101 254-256° C.Dibenz(a,h)anthracen-7-ol naphtho[1,2-b]phenanthren-7-ol 63041-68-9 102254-256° C. Glycosminine 2-(phenylmethyl)-1H- 4765-56-4 (248-249°)quinazolin-4-one 103 254° C. 2-Anthracenol (9Cl) anthracen-ol 613-14-9104 254-256° C. 4-Amino-5-cyanopyrimidine 4-aminopyrimidine-5-16357-69-0 carbonitrile 105 254° C.; 2-Amino-4-nitrobenzothiazole4-nitro-1,3-benzothiazol-2- 6973-51-9 (233°) amine 106 255-256° C.2,4,6,8-Tetraphenyl-3,7- 2,4,6,8-tetra(phenyl)-3,7- 37123-09-4(250-252°) diazabicyclo [3.3.1]nonan-9- diazabicyclo[3.3.1]nonan-9- oneone 107 255-257° C. Tetrahydro-5,5-dimethyl-5,5-dimethyl-1,3-diazinan-2- 17496-93-4 2(1H)-pyrimidinone one 108 255°C. Benzoic acid 2- (benzoylamino)urea 2845-79-6(aminocarbonyl)hydrazide, 9Cl 109 255-258° C. 2,4,6-Quinazolinetriaminequinazoline-2,4,6-triamine 13741-90-7 110 255-256° C.3-Cyanothioxanthone 9-oxothioxanthene-3- 51762-90-4 carbonitrile 111255-256° C. 6-Nitrobenzo[a]pyrene 6-nitrobenzo[b]pyrene 63041-90-7 112255° C. 3-Methyl-1,2,4-triazolo[4,3- 3-methyl-[1,2,4]triazolo[4,5-65267-32-5 a]pyrimidine a]pyrimidine 113 255° C.2-Methyl-4(5)-nitroimidazole 2-methyl-4-nitro-3H-imidazole 696-23-1 114255-257° C. 4-Hydroxy-2-phenylquinoline 2-phenyl-1H-quinolin-4-one14802-18-7 115 255-256° C. Halfordinol 4-(2-pyridin-3-yl-1,3-oxazol-5-4210-82-6 yl)phenol 116 256-258° C. Tetra-4-pyridinylthiophene4-[2,4,5-tri(pyridin-4- 64048-12-0 yl)thiophen-3-yl]pyridine 117256-258° C. Nifenazone N-(1,5-dimethyl-3-oxo-2- 2139-47-1phenylpyrazol-4-yl)pyridine-3- carboxamide 118 256-257° C. IndisetronN-(3,9-dimethyl-3,9- 141549-75-9 diazabicyclo[3.3.1]nonan-7-yl)-1H-indazole-3-carboxamide 119 256° C. 1,2,3-Indanetrioneindene-1,2,3-trione 938-24-9 (241-243°) 120 256-258° C.1,4-dimethylquinoxaline-2,3- 1,4-dimethylquinoxaline-2,3- 58175-07-8dione dione 121 256-258° C. 2-aminopyridin-1-ium-4-2-aminopyridin-1-ium-4- 13538-42-6 carboxamide carboxamide 122 257-258°C. Terosite 4-phenyl-2,6-bis(4- 24368-63-6 phenylpyridin-2-yl)pyridine123 257° C. Pentaphene Pentaphene 222-93-5 124 258-259° C.Tetrahydrolathyrine 2-amino-3-(2-amino-3,4,5,6- 72748-96-0tetrahydropyrimidin-4- yl)propanoic acid 125 258-260° C. QuinezamideN-(5-methylpyrazolo[1,5- 77197-48-9 c]quinazolin-1-yl)acetamide 126 258°C. 1,10-Phenanthroline-5,6- 1,10-phenanthroline-5,6-dione 27318-90-7dione 127 258° C. 2-Nitrobenzimidazole 2-nitro-1H-benzimidazole5709-67-1 128 258-259° C. 1H-imidazo[5,4-b]pyrazine1H-imidazo[5,4-b]pyrazine 273-94-9 129 258-260° C. Magnosprengerine4-(2-dimethylaminoethyl)-2- 35266-63-8 methoxyphenol 130 258-259° C.Dibenz(a,h)anthracen-6-ol naphtho[4,3-b]phenanthren- 83710-52-5 13-ol131 258-260° C. 6-Amino-5,8-quinolinedione 6-aminoquinoline-5,8-dione24149-57-3 132 259-260° C. 7h-Pyrido[4,3-c]carbazole7H-pyrido[4,3-c]carbazole 205-29-8 133 259° C. 2-Methyl-9H-carbazole2-methyl-9H-carbazole 3652-91-3 134 259-260° C.4,6-dimethyl-2-sulfanylidene- 4,6-dimethyl-2-sulfanylidene- 54585-47-61H-pyridine-3-carbonitrile 1H-pyridine-3-carbonitrile 135 259-261° C. CV399 4-methoxy-6-methyl-1,3,5- 1668-54-8 triazin-2-amine 136 259-260° C.6-(4-aminobutyl-ethylamino)- 6-(4-aminobutyl-ethylamino)- 66612-29-12,3-dihydro-1,4- 2,3-dihydrophthalazine-1,4- phthalazinedione dione 137259-260° C. 2-(1(2H)- 2-acenaphthen-1- 477-77-0Acenaphthylenylidene)-1(2H)- ylideneacenaphthen-1-one acenaphthylenone138 260-261° C. Diphenylene dioxide 2,3- oxanthrene-2,3-dione 6859-47-8quinone 139 260° C. Benzo(a)pyrene-7,8-dione benzo[a]pyrene-7,8-dione65199-11-3 140 260-265° C. 2-Adamantanol adamantan-2-ol 700-57-2 141260-263° C. Friedelan-7-one (4S,4aR,6aS,6aS,6bR,8aR,12aR,- 18671-54-014aS,14bR)- 4,4a,6a,6b,8a,11,11,14a- octamethyl-2,3,4,5,6a,7,8,9,10,12,12a,13,- 14,14b-tetradecahydro-1H- picen-6-one142 260-261° C. 1,2-Chrysenedione chrysene-1,2-dione 2304-83-8 143260-262° C. benzo[a]anthracene-5,6- benzo[c]anthracene-5,6-dione18508-00-4 dione 144 260° C. Pentaerythritol 2,2- 115-77-5bis(hydroxymethyl)propane- 1,3-diol 145 260-265° C. 1-Methylcytosine4-amino-1-methylpyrimidin-2- 1122-47-0 one 146 260° C.2,8-Dihydroxyquinoline 8-hydroxy-1H-quinolin-2-one 15450-76-7 (297-299°)147 260-262° C. N(beta)-Alanyl-1-methyl- 3-aminopropanoyl (2S)-2-331-38-4 histidine amino-3-(1-methylimidazol-4- yl)propanoate 148261-263° C. Sporidesmolide I 4,19-dimethyl-3,12-bis(2- 2900-38-1methylpropyl)-6,9,15- tri(propan-2yl)-1,10-dioxa4,7,13,16-tetrazacycloicosane- 2,5,8,11,14,17-hexone 149 261-264° C.Picodralazine [4-(pyridin-4- 17692-43-2 ylmethyl)phthalazin-1-yl]hydrazine 150 261-262° C. 8-Phenyl-1H-purine 8-phenyl-7H-purine4776-14-1 151 261° C. Furagin 1-[[(E)-3-(5-nitrofuran-2- 1672-88-4yl)prop-2- enylidene]amino]imidazolidine- 2,4-dione 152 261° C.4,8-Dibenzoyl-5-methoxy-1- 2-(piperidin-1-ylmethyl)- 372520-17-7naphthalenol 10,10a-dihydro-5H- imidazo[1,5-b]isoquinoline-1,3- dione153 261-262° C. beta-Carboline-3-carboxylic methyl9H-pyrido[5,4-b]indole- 69954-48-9 acid methyl ester 3-carboxylate 154261° C. 1,4-Bis(2- 2-methyl-N′-(2-oxoindol-3- 5153-65-1benzothiazolyl)benzene yl)benzohydrazide 155 261° C.12H-[1]Benzopyrano[2,3- chromeno[3,2-b]quinoxalin-12- 82501-03-9b]quinoxalin-12-one one 156 261-262° C. Indeno(1,2-c)isochromene-indeno[3,2-c]isochromene- 5651-60-5 5,11-dione 5,11-dione 157 261-263°C. Benzene-1,3,5-tricarbonitrile benzene-1,3,5-tricarbonitrile10365-94-3 (254-258°) 213.5-214°  (210-212°) 158 262-263° C. Guanazine1,2,4-triazole-3,4,5-triamine 473-96-1 159 262° C. Razobazam3,8-dimethyl-4-phenyl-2H- 78466-98-5 pyrazolo[3,4-b][1,4]diazepine-5,7-dione 160 262° C. 1-Phenylbarbituric acid1-phenyl-1,3-diazinane-2,4,6- 15018-50-5 trione 161 262-263° C.6-Methoxypurine 6-methoxy-7H-purine 1074-89-1 162 262° C. N-(4-chloro-2-N-(4-chloro-2- 5356-56-9 (283-286°) nitrophenyl)thiophene-2-nitrophenyl)thiophene-2- carboxamide carboxamide 163 262-262.5° C.9H-Fluorene-4-carboxylic 7-nitro-9-oxofluorene-4- 42523-38-6 acid,7-nitro-9-oxo- carboxylic acid 164 262° C. 4-Nitroacridone4-nitro-10H-acridin-9-one 4261-62-5 165 262-264° C. Papyriogenin A(4aR,6aR,6aS,6bR,8aR,12aS)- 59076-79-8 2,2,6a,6b,9,9,12a-heptamethyl-3,10-dioxo- 1,4,5,6,6a,7,8,8a,11,12- decahydropicene-4a-carboxylic acid 166 262-264° C. N-[(1R,3S)-3- N-[(1R,3S)-3- 32189-20-1acetamidocyclohexyl]acetamide acetamidocyclohexyl]acetamide 167 262-263°C. 1,3-Di-p-tolylurea 1,3-bis(4-methylphenyl)urea 621-00-1 168 263-265°C. 1,1,3,3- propane-1,1,3,3- 10550-79-5 Propanetetracarboxamidetetracarboxamide 169 263° C. 5-Hydroxy-4-methyl-2H-1-5-hydroxy-4-methylchromen-2- 2373-34-4 benzopyran-2-one one 170 263-264°C. 1,3-Dihydro-5-methoxy-2H- 5-methoxy-1,3- 37052-78-1benzimidazole-2-thione dihydrobenzimidazole-2-thione 171 263° C.9,10-Dinitroanthracene 9,10-dinitroanthracene 33685-60-8 (288-290°)(294-296°) 172 263-270° C. Mdl 74366 [2-(2-dimethylaminoethyl)-128008-98-0 2,5,7,8-tetramethylchroman-6- yl] acetate hydrochloride 173263-264° C. Dibenz(a,h)anthracen-5-ol naphtho[4,3-b]phenanthren-4002-76-0 12-ol 174 263-265° C. Paxillarine A [(4R,8R,10R,13S,17S)-3-145022-89-5 (benzoyl-methylamino)-17-(1- dimethylaminoethyl)-16-hydroxy-10,13-dimethyl- 2,3,4,5,6,7,8,9,11,12,14,15,16,-17-tetradecahydro-1H- cyclopenta[a]phenanthren-4-yl] acetate 175263-267° C. N-Deacetyl-3-demethyl-N- N-(3-hydroxy-1,2,10- 18172-26-4formylcolchicine trimethoxy-9-oxo-6,7-dihydro 5H-benzo[d]heptalen-7-yl)formamide 176 263-264° C. N-[(2S,4aR,6S,7R,8R,8aS)-8-N-[(2S,4aR,6S,7R,8R,8aS)-8- 13343-63-0 hydroxy-2-phenyl-6-hydroxy-2-phenyl-6- (phenylmethoxy)- (phenylmethoxy)- 4,4a,6,7,8,8a-4,4a,6,7,8,8a- hexahydropyrano[5,6- hexahydropyrano[5,6-d][1,3]dioxin-7-yl]acetamide d][1,3]dioxin-7-yl]acetamide 177 263° C.7-Amino-5,8-quinolinedione 7-aminoquinoline-5,8-dione 64636-91-5 178263-264° C. 9-Acridinecarboxamide acridine-9-carboxamide 35417-96-0 179264° C. Theophylline 1,3-dimethyl-7H-purine- 58-55-9 (268°) 2,6-dione180 264-265° C. Siguazodan 3-cyano-2-methyl-1-[4-(4- 115344-47-3methyl-6-oxo-4,5-dihydro- 1H-pyridazin-3- yl)phenyl]guanidine 181 264°C. 4-nitro-N-(pyridin-2- 4-nitro-N-(pyridin-2- 70421-66-8ylmethylideneamino)aniline ylmethylideneamino)aniline 182 264-266° C.3-(Hydroxyamino)-1H-isoindol-1- 3-(hydroxyamino)isoindol- 29833-90-7 one1-one 183 264° C. 2,3-Diaminophenazine phenazine-1,2-diamine 655-86-7184 264-265° C. Harmine 7-methoxy-1-methyl-9H- 442-51-3pyrido[3,4-b]indole 185 264-265° C. 2-Hydroxyisophenoxazin-3-one10H-phenoxazine-2,3- 1915-49-7 dione 186 264-265° C.3-Hydroxyestra-1,3,5(10),6- (8R,9S,13S,14S)-3- 2208-12-0 tetraen-17-onehydroxy-13-methyl- 9,11,12,14,15,16- hexahydro-8H-cyclopenta[a]phenanthren- 17-one 187 264-268° C.21-Hydroxyfriedelan-3-one (4R,4aS,6aS,6aS,6bR,8aS, 59995-80-110R,12aR,14aS,14bS)- 10-hydroxy- 4,4a,6a,6b,8a,11,11,14a- octamethyl-2,4,5,6,6a,7,8,9,10,12,12a, 13,14,14b-tetradecahydro- 1H-picen-3-one 188264-266° C. 9-octyl-3H-purine-6-thione 9-octyl-3H-purine-6-thione60632-18-0 189 265° C. 3,4,5-tri(phenyl)-1H-pyrazole3,4,5-tri(phenyl)-1H- 18076-30-7 pyrazole 190 265-268° C.Spirobishexahydropyrimidine 4,4,10,10-tetramethyl- 4115-66-6 1,3,7,9-tetrazaspiro[5.5]undecane- 2,8-dione 191 265-267° C.1,2,3,4-tetrahydroacridine-9- 1,2,3,4-tetrahydroacridine- 42878-53-5carboxamide 9-carboxamide 192 265-266° C. 1H-Pyrrolo(2,3-d)pyrimidine-1,3,7-trimethylpyrrolo[3,2- 39930-51-3 2,4(3H,7H)-dione,e]pyrimidine-2,4-dione 1,3,7-trimethyl- 193 265° C.4-(4-carbamoylphenoxy)benzamide 4-(4-carbamoylphenoxy)benzamide6336-34-1 194 265-266° C. 4,4′-Iminobisbenzonitrile 4-[(4- 36602-05-8cyanophenyl)amino]benzonitrile 195 265-266° C. 1,10-Phenanthroline,5,6-dimethyl-1,10- 3002-81-1 5,6-dimethyl- phenanthroline 196 265-267°C. 4H-1-Benzopyran-4-one, 7-hydroxy-2-(4- 487-24-17-hydroxy-2-(4-methoxyphenyl)- methoxyphenyl)chromen- 4-one 197 265° C.1,4,6-triaminopyrimidine-2-thione 1,4,6-triaminopyrimidine-2- 4765-63-3thione 198 265° C. 9,10-Anthracenedione, 1,8-diaminoanthracene- 129-42-01,8-diamino- 9,10-dione 199 265° C. 2-hydroxy-1H- 5690-46-0benz[de]isoquinoline- 1,3(2H)N-dione, 9Cl; Naphthalhydroxyamic acid 200265° C. 3-aminoquinoxaline-2-carboxamide 67568-30-3 Amide derivative 201265° C. 6-Nitro-2-quinolinamine 49609-07-6 202 265° C.2-aminonaphtho[2,1d] thiazole 54380-14-2 (N—Ac form) 203 265° C.hernandonine, deriv 3-methoxy 155944-22-2 204 265° C.3-hydroxy-6-methylisoquinoline 51463-11-7 205 265° C.hexahydro-1,2,4-ethanylylidene- 110243-21-51H-cyclobuta[cd]pentalene-3,5,7- trione 206 265° C. 2,6-anthracenediol,13979-53-8 di-Ac form 207 265° C. 1H,9H-pyrrolo[3,2- 147345-48-0b][1,4]benzoxazin-2(3H)-one 208 265° C. Histidine phenylalanineanhydride 56586-95-9 (−)-cis-form 209 265° C. 2,4,5,6,7-pentamethyl-1H-69700-34-1 benzimidazole 210 265° C. 3-[2-(4-pyridinyl)ethenyl]-1H-53645-38-8 indole (E)-form 211 265° C. 9-aminofluorene (N—Ac form)5424-77-1 212 265° C. pyrido[2,3-b]pyrazine-2,3-diolC₇H₅N₃O₂/c11-6-7(12)10- 2067-84-7 (derivative 3-Et ether)5-4(9-6)2-1-3-8-5/h1- 3H,(H,9,11)(H,8,10,12) 213 265° C. diamidederivative 13363-51-4 (C₈H₈N₂S₂) 214 265° C. 2,4-dinitrophenylhydrazoneNot Available (derivative of 1-(1H-inden-6- yl)ethanone chloride 215265° C. Tricarbazyl 6515-02-2 3-(9-Carbazoly1)-9,9′ dicarbazole

In certain aspects, the one or more organic compounds or chemicals areprocessed to minimize evaporative loss, enhance crystallinity, and toobtain high purity levels. The one or more organic compounds areprocessed into compacted shapes, such as pellets or grains, byapplication of pressure in a die or mold, by way of example. Thestructural integrity of pellets is desirably sufficient to withstandcompressive forces of the HTTCO device, for example to withstand theapplied force and bias to the HTTCO springs and encasement in a HTTCOassembly. The unique ability of HTTCO's to maintain physical rigidityand spring compression and therefore maintain electrical continuity atTCO operating temperatures in a high temperature device, yet furtherhaving the ability to physically transition and open the circuit at arated threshold temperature is an important feature of thehigh-temperature thermal pellet compositions of the present teachings.By way of example, as noted previously, certain HTTCOs are capable ofwithstanding extended exposure to operating temperatures up to about 5°C. below the threshold or actuation temperature without breaking theelectrical continuity of the circuit.

The high temperature thermal pellet compositions can be manufacturedinto any commercially available form suitable for use inside a housingof a TCO, including granules, pellets, spheres and any geometric shapeknown to those in the art. In addition to the above described organiccompounds, the high temperature thermal cutoff pellet compositions ofthe present disclosure may optionally include one or more componentsselected from the group consisting of: a binder, a press aid, a releaseagent, a pigment, or mixtures thereof. The binder component, whichgenerally softens (melts) at a temperature below the melting point ofthe organic component, is primarily utilized to assist in the productionof pellets. While various binders known for pellet formation can beutilized, suitable binders include polyethylene glycol, 1,3-benzenediol,epoxies, polyamides and mixtures thereof. The binder is generallypresent in amounts up to about 10 wt. % based on the total composition.

Additionally, it may be desirable to employ a lubricant or pressing aidto aid in flowing and fill properties when processing the thermalpellets. For example, among the numerous lubricants or press aids whichhave proven useful are calcium stearate, boron nitride, magnesiumsilicate and polytetrafluoroethylene (Teflon®), among others. Thelubricant is generally present in an amount up to about 5 wt. % based onthe total pellet composition. It may also be desirable under certainapplications to incorporate coloring agents such as pigments into thethermal cutoff composition to allow for rapid visual inspection of thepellets condition. Virtually any known pigment which is compatible withthe aforementioned thermal cutoff composition components may beemployed. Pigments, when employed, are typically present in an amount upto about 2 wt. % of the pellet composition.

In certain embodiments, the pellet composition may consist essentiallyof a single organic composition as the primary ingredient to arrive at atransition temperature of greater than or equal to about 240° C., andoptionally a binder, optionally a press aid, optionally a release agent,and/or optionally a pigment. Such a pellet composition may compriseminimal amount of diluents or impurities that do not substantiallyaffect the transition temperature of the pellet composition or theperformance of the HTTCO at operating temperatures above the thresholdtemperature.

Initially, a first high-temperature thermal pellet sample can beprepared with the objective of obtaining a product having an expectedtransition temperature (e.g., melting point temperature or melttransition temperature) of about 240° C. The sample is processed toenhance the crystallinity and then prepared by mixing between about 90%to about 100% by weight of chemical either alone or with 10% to about0.25% by weight of additives such as binders in a hammermill mixer.Added to the aforementioned organic compounds may be 5% to 0.25% byweight of a binders, such as polyamide binder, among others and 1% to0.05% by weight of an organic azo pigment. The resulting compositionexhibits a transition temperature/melting point temperature of about236° C.

Additional samples can be prepared to make a HTTCO product having amelting point temperature of about 257° C. In this regard, the sample isprocessed to enhance the crystallinity and then prepared by mixingbetween about 90% to about 100% by weight of chemical either alone orwith 10% to about 0.25% by weight of additives, such as binders, in ahammermill mixer. Added to the aforementioned organic compounds may be5% to 0.25% by weight of binders, such as polyamide binder, among othersand 1% to 0.05% by weight of an organic azo pigment. After blending tohomogenize the constituent components, the sample may be analyzed usingdifferential scanning calorimetry (DSC). The resulting composition has atransition temperature/melting point temperature of about 257° C.

In addition to exhibiting repeatable transition temperatures, thehigh-temperature thermal cutoff compositions of the present disclosureare also expected to exhibit clean current interrupt properties,decreased material and processing costs, and should have flexibility topermit customized design of predetermined thermal cutoffs to specificcustomer needs. In certain aspects, high melting point organiccompositions can be formulated by use of computer software to calculatemelting points of organic compounds for example, such as the computerprogram sold under the tradename PROMA2000®, manufactured by DaijinTechnologies Corp. South Korea.

Furthermore, the transition temperatures/melting points of the variouscompositions to be used in the thermal cutoff composition in the presentdisclosure can be measured using ThermoGravimetric Analyzers coupledwith and without Mass Spectrometer (TGA-MS), differential scanningcolorimetry (DSC) and differential thermal analysis (DTA), by way ofexample. Devices for performing these qualitative and quantitativeassays are commercially available, for example, from TA Instruments, NewCastle, Del. USA, Model Q2000 (DSC), and Mettler STARe ThermoGravimetricAnalyzer, TGA/sDTA851e, coupled to a Balzers ThermoStar MassSpectrometer from Mettler-Toledo, Columbus, Ohio. Further, thecompositions of the present teachings can be quantitatively analyzedusing known techniques such as proton or carbon nuclear magneticresonance, mass spectroscopy or Fourier transform infrared spectroscopytechniques, by way of non-limiting example.

High-Temperature Sealants

In various embodiments of the present invention, the high temperatureTCO device comprises a high-temperature sealant system that is used overone of more openings in the housing to provide a barrier between theinterior of the HTTCO and the external atmosphere. In various aspects,the high temperature sealant system or seal is robust, reliable, andmaintains integrity as high operating temperatures of the HTTCO device.The seal is an important aspect of the reliability and longevity of theHTTCO device, in that selection of an appropriate seal material providesa barrier that maintains chemical equilibrium inside the HTTCO, even atthe high operating temperatures of the HTTCO and prevents substantialloss of the pellet materials through the seal or barrier.

Thus, in various aspects, the seal material system provides a strongsealing mechanism over one or more openings in the housing to preventundesirable thermal pellet sublimation, and thus, loss of pelletmaterial. In certain aspects, the reliability of the HTTCO sealingsystem can be related to the lifespan of the HTTCO device, where apredetermined life span is at least 1,000 hours or longer at 235° C.(reflecting the operating temperatures of about 5° C. than the thresholdrating temperature of 240° C.).

In certain aspects, the high-temperature seal system is an epoxy-basedsystem that is cured to provide a durable, high-temperature, strongsealing mechanism. One particularly suitable high temperature resistantepoxy system is formed from precursors comprising one or more diglycidylether of bisphenol A resins, which are combined with a hardener, forexample a modified imidazole hardener or epichlorhydrin.

In various embodiments, the epoxy systems of the present invention aregenerally prepared in accordance with the manufacturer'srecommendations. In certain embodiments, the epoxy systems are preparedin a modified manner to facilitate curing of the epoxy system in amanner that produces a strong mechanical seal between the HTTCOcomponents (both metal and ceramic), which can withstand temperaturesabove about 235° C., optionally above about 240° C., optionally aboveabout 245° C., optionally above about 250° C., optionally above about260° C., optionally above about 265° C., optionally above about 270° C.,optionally above about 275° C., optionally above about 280° C.,optionally above about 285° C., optionally above about 290° C., and incertain aspects, optionally up to about 300° C., in a manner capable ofretaining a stable thermal pellet composition and preventing substantialsublimation of the thermal pellet composition. In some embodiments, theepoxy systems of the present invention are cured to B-stage and/or fulladvanced or accelerated cure stage at various temperatures and relativehumidity suitable to create the desired barrier seal. In certainaspects, the B-stage epoxy cure is a low temperature cure typicallyperformed at less than or equal to about 60° C. at various relativehumidities ranging from about 0% to about 85%, optionally at about 0 toabout 75%, optionally about 0 to about 50%, optionally about 0 to about40%, and in certain aspects about 0 to about 35%. A polymer seal isgenerally considered to be B-stage cured when the seal has a hardnessshown by impression of a permanent indent mark at Shore Durometer 75.Thus, in certain aspects, the curing is conducted to achieve a hardnessof at least Shore D 75. In certain embodiments, an accelerated oradvanced cure is conducted after B-stage curing of the HTTCO device atan elevated temperature, for example from about 150° C. to about 175° C.for 3 to 5 hours, by way of example.

Many commercially available epoxy-based systems include at least two tothree curable precursors that are mixed together and then cured to forma polymer. In certain embodiments, one suitable high-temperatureepoxy-based sealant system to form a seal in the HTTCO comprisesprecursors comprising a diglycidyl ether bisphenol A resin and ahardener. In certain aspects, such a hardener comprises a modifiedimidazole compound. In certain embodiments, the hardener comprises a2-ethyl-4-methyl-1H-imidazole. In certain embodiments, the epoxy-basedsealant is formed by combining at least two epoxy precursors, where afirst precursor comprises at least one epoxy resin, such as a bisphenolA diglycidyl ether, an elastomer polymer, and neopentyl glycoldiglycidyl ether; and a second precursor comprises2-ethyl-4-methyl-1H-imidazole as the hardener. By way of example, acommercially available diglycidyl ether of bisphenol A and modifiedimidazole hardener system is commercially available from Henkel Loctiteas the following: Loctite® Hysol® 210210 Epoxy Resin Part A (Item No.36745), Loctite® Hysol® 210211; Epoxy Hardener Part B (Item No. 36746);and Loctite® Hysol® 210209 Epoxy Pigment (Item No. 36745) (this combinedepoxy system is referred to as “C5 epoxy”). Loctite® Hysol® 210210 EpoxyResin Part A contains about 60-100% by weight of a first proprietaryepoxy resin, which is believed to be a modified bisphenol A diglycidylether epoxy resin 10-30% of a second proprietary epoxy resin, which isalso believed to be a modified bisphenol A diglycidyl ether, 10-30% ofneopentyl glycol diglycidyl ether (CAS No. 17557-23-2); 5-10% of aproprietary elastomer, 1-5% titanium dioxide pigment, and 1-5% amorphousfumed silica. Loctite® Hysol® 210211 Epoxy Resin Part B contains 60-100%by weight of a proprietary modified imidazole, which is believed to be2-ethyl-4-methyl-1H-imidazole. Loctite® Hysol® 210209 Epoxy Resin Part Ccontains 30-60% by weight titanium dioxide, 10-30% of a firstproprietary epoxy resin, which is believed to be a modified bisphenol Adiglycidyl ether epoxy resin, 10-30% of a second proprietary epoxyresin, which is also believed to be a modified bisphenol A diglycidylether, and 1-5% of a third proprietary epoxy resin, which is alsobelieved to be a modified bisphenol A diglycidyl ether epoxy, 1-5%neopentyl glycol diglycidyl ether, 1-5% alkyl glycidyl ether, 1-5%aluminum oxide, 1-5% fumed amorphous silica, and lastly 1-5% of aproprietary elastomeric polymer.

In preparing the C5 epoxy, 80-100 parts by weight of the resin Part A ismixed with 0-20 parts by weight for the hardener Part B. Part C isoptional and can be added at 0-20 parts by weight to form the final C5epoxy to be applied to the TCO components for sealing the devicecontaining the thermal pellet composition.

In yet another embodiment, an epoxy-based sealant is formed by combiningat least two precursors, wherein a first precursor comprises an epoxyresin or bisphenol A diglycidyl ether polymer; a second precursorcomprises a hardener or curing agent, such as1-(2-cyanoethyl)-2-ethyl-4-methyl imidazole; and a third precursorcomprises catalysts includingbenzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride,and phthalic anhydride.

After the curable epoxy-based material has been applied to seal the TCOcomponents to seal one or more openings (such as shown in FIGS. 1-2),the epoxy-based sealant system is optionally cured. Curing can beconducted by any means known in the art, including by application ofheat, actinic radiation, and the like. In certain aspects, the epoxysealant materials are subjected to a B-stage cure, where the epoxysystem is heated to a temperature range of about 45° C. to about 65° C.in a controlled atmosphere having relative humidity ranging from 0% to80%. Optionally, a full advanced cure can be conducted after B-stagecuring. An advanced cure is optionally conducted at a temperature rangeof about 150° C. to about 200° C. in a controlled atmosphere havingrelative humidity ranging from 0% to 5%. In certain aspects, the C5epoxy seal material is cured by placing the HTTCO device in an oven andheating the TCO at 248° C. for about 3 to about 9 hours at 0% relativehumidity.

In certain other embodiments, the HTTCOs can be sealed with a suitableepoxy-based system commercially available from Emerson & Cuming Corp.,Billerica, Mass. USA, which is a bisphenol A diglycidyl ether polymer(Part A); an epichlorohydrin hardener (Part B); and a catalyst (Part C)sold under the trade name Stycast® W 66 epoxy system (herein referred toas the “W66 epoxy system”). Specifically, the W66 epoxy system includesPart A comprising Bisphenol A diglycidyl ether polymer having an averagemolecular weight of less than 700 at 100 wt. %, Part B comprising1-(2-cyanoethyle)-2-ethyl-4-methyl Imidazole hardener at greater than 99wt. % in less than 0.1% acrylonitrile carrier. Part C of the W66comprises a catalyst of Benzenetetracarboxylic-1,2,4,5-Dianhydride(35-50% by weight), Hexahydrophthalic anhydride (35-50% by weight) andphthalic anhydride (1-5% by weight).

In preparing the W66 epoxy, part A in an amount ranging from 50% toabout 80% by weight is mixed with part B in an amount ranging from 50%to about 20% by weight and mixed. Once the W66 epoxy system has beenapplied to seal the HTTCO components, the W66 epoxy is optionally curedto a B-stage and/or advanced cure. By way of non-limiting example, theW66 seal system is applied and cured by placing the device in acontrolled atmosphere and heating the TCO at 40° C. for about 48 toabout 96 hours at 35% to 85% relative humidity.

Example 1

In accordance with various aspects of the present disclosure, a hightemperature TCO device is formed as follows. A pellet is formed bymixing 980 g to 1000 g of triptycene (commercially available fromSigma-Aldrich manufacturer at 95% to 99% purity) with 20 g to 0.5 g ofcolorants, binders, and or release agents. The homogenized mixture isprocessed on a standard powder compaction press widely available frompharmaceutical equipment suppliers. The powder is fed through a gatedpowder flow control system and spread evenly over a rotary die table.The powder fills the dies and punches press the powder in the dies underapproximately 1 ton to 4 tons pressure to form a compacted powder pellethaving a density of 29 pellets per gram to 50 pellets per gram. Thepellet is placed into a high-conductivity metal, closed-end cylinderwith an inner diameter approximately the outer diameter of the TCOpellet. The closed end of the cylinder is staked shut with an axialconductive metal lead protruding out of the cylinder. Other componentsare loaded atop the pellet in a stacked fashion depending on the end-userequirements of the TCO. A sub-assembly comprised of a non-conductiveceramic bushing with an axial bore hole and a conductive metal leadwhich has been inserted in the open bore and mechanically restrainedinto a permanent one-piece assembly by deformation of the metal lead isinserted into the open end of the TCO cylinder. The stacked componentsnoted earlier in paragraph 0018 are compressed into the cylinder by theceramic, isolated lead assembly and the rim of the open end of thecylinder is mechanically rolled over the ceramic bushing to permanentlyenclose the internal components in the TCO cylinder. The closed TCO isthen sealed with a high temperature, epoxy sealant. An epoxy-basedsealant is prepared at 25° C. to seal the bushing and isolated lead androlled over cylinder edge exterior terminal region of the TCO housing bymixing 200 g of LOCTITE® HYSOL® 210210 Epoxy resin Part A (an epoxyresin comprising bisphenol A and diglycidyl ether); 14 g of LOCTITE®HYSOL® 210211 Epoxy hardener Part B (an imidazole hardener); andoptionally 13.2 g of LOCTITE® HYSOL® 210209 Epoxy pigment Part C (epoxyresins, neopentyl glycol diglycidyl ether, pigment, . . . ) or anadditional 13.2 g of LOCTITE® HYSOL® 210210 Epoxy resin Part A in asealed paddle mixer at 100 RPM for 10 minutes under vacuum to 30 mmHg toform a uniform epoxy mixture. The reagents are mixed for a total of 1.5minutes to 5 minutes with a 10 minute no-mix vacuum step at the end ofthe mechanical mix to form a single component matrix mixture. The epoxymixture is applied over the bushing and isolated lead to cover down tothe rolled over cylinder rim of the TCO device using epoxy dispenserbottles with narrow tips or mechanical application equipment to ensureeven coverage.

The assembled TCO having the epoxy sealing compound applied is thencured for 9 hours at 48° C. to 60° C. under 0% RH to 85%. The B-stagedTCO assemblies are then cured in a controlled over at a temperature of150° C. optionally up to 235° C. in 0% RH to 35% RH for 3 hours up to 6hours.

The C5 epoxy system is studied to demonstrate the high-temperatureperformance of the sealant system, as well as the ability to retainpolycyclic organic compounds of the pellet of the HTTCO device.Specifically, the high-temperature thermal pellet contained triptyceneand a polytetrafluoroethylene release agent, which was retained by theC5 epoxy seal during continuous exposure to 247° C. A thermal pelletformed of a smaller molecule pentaerythritol (CAS No. 115-77-5) having amelting point beginning at 259° C. was not retained in a TCO using theC5 sealing system during continuous exposure to 247° C. The meltingpoints of the two pellet organic compounds, triptycene andpentaerythritol are similar, and, are known to have similar volatileevolution behavior. However, the C5 sealing system is able to retain thetriptycene inside the sealed HTTCO housing significantly better than thepentaerythritol.

The pellet height of the pentaerythritol at Day 1 goes from an initialpellet height of 101 thousandths of an inch to 0.00 thousandths of aninch. Thus, TCOs having the pentaerythritol open continuity or exhibitedresistance greater than 200 kOhm (actuate) almost immediately. The HTTCOhaving a pellet containing triptycene has an initial pellet height ofabout 98 thousandths of an inch and retains at least 80 thousandths ofan inch pellet height for at least 13 weeks and does not exhibitresistance of greater than 200 kOhm until over 2,100 hours ofperformance for 9 out of 10 HTTCO samples.

Given that the compounds melting points and their volatility onset byTGA are nearly identical, the difference in retention is believed to beattributed to functionality or size of the molecule, or a combination ofboth. Using a simple computer model, the sizes (radii) of the compoundsare calculated. As noted in Table 3, below, triptycene has a radius of0.46 nm while pentaerythritol has a radius of 0.33 nm. Also, thetriptycene molecule is fairly rigid given the steric hindrance of thethree benzene rings. When viewed along the end of the molecule, the 3benzene molecules separate at 120° from each other for maximum spacing.On the other hand, the pentaerythritol has significantly more molecularfreedom to twist and reorient itself. The triptycene has littlefunctionality other than the double bonds present in the aromatic ring.However, the aromatic rings have the ability to pi-pi stack with otheraromatic rings in the epoxy structure, which could immobilize them inthe pores thus blocking the pore. The pentaerythritol has four polarhydroxyl bonds that have hydrogen bond accepting/donating capability.

TABLE 3 Compound triptycene pentaerythritol CAS # 477-75-8 115-77-5Other Names Triptyceue; Methane tetramethylol; 9,10-o-Benzenoanthracene,9,10- Pentaerythrital: dihydro-; Tetrahydroxymethylmethane;Tribenzobicyclo[2.2.2]octatriene: Tetrakis(Hydroxymethyl)methane;Tryptyceue; Tetramethylolmethane; Anthracene, 9.10-dihydro-9,10-2,2-Bis(hydroxymethyl)-1,3-propanediol: O-benzeno- Methane,tetrakis(hydroxymethyl)-, Formula C₂₀H₁₄ C₅H₁₂O₄ F.W. 254.33 136.15Melting Point 252-256° C. 257-264° C. 251-254° C. 253-258° C. BoilingPoint None found 276° C. (at 30 mmHg) 276° C./30 mmHg(lit.) VaporPressure None found <1 mmHg (20° C.) radius 4.7 Angstroms 3.3 AngstromsStructure

A 1-aminoanthraquinone [CAS #82-45-1] pellet is also examined for itsbehavior in a C5 epoxy sealing system. The 1-aminoanthraquinone has amelting point in the same range as the pentaerythritol and triptycene,so once again the size and functionality are examined to provide insightinto the interaction of the organic compound with the cured epoxy sealmaterial. The 1-aminoanthraquinone molecule lies in a single plane andis a rigid molecule due to the benzene rings and the carbonyl bonds thatbond them together—all of which require planar orientation. The radiusof the 1-aminoanthraquinone is 0.45 nm, which is similar in size to thetriptycene. However, the 1-aminoanthraquinone has the added advantage ofhaving more functionality present with which to interact with the epoxyseal material. The carbonyl bonds can accept hydrogen donation and theamine group can hydrogen donate/accept. Based on its steric similarityto triptycene and its functionality similarity to pentaerythritol,1-aminoanthraquinone has even greater retention by the epoxy seal thatthe triptycene or pentaerythritol.

Specimens of the C5 system are produced by reacting the components attemperatures and humidities listed below. All specimens are exposed tothe same temperature programming for B-staged and advanced cure levels.B-staged specimens are heated at 48° C. for 5 hours and then at 58° C.for 4 hours. The B-staging is performed in two different relativehumidity environments (0% and 35% RH) to determine the effect of wateron the B-stage curing. Specimens exposed to 35% RH are B-staged in ahumidity chamber that maintains the humidity at 35% while following thetemperature program. Specimens prepared in 0% RH are B-staged in anoven. To achieve 0% RH, a compressed air source with two water traps isemployed to ensure that no water is exposed to the epoxy system duringB-staging. Some specimens required advanced curing, which entailedheating the B-staged specimens to 150° C. for 3 hours. The humidity isnot monitored during advanced curing, but the specimens are stillidentified by their B-stage humidity level for labeling purposes.

From the surface area data, both cured epoxy seal samples have very lowsurface areas (approximately 0.09 m²/g), and the shapes of theadsorption plots indicate a very nonporous structure. By dividing thevolume of the pores by their area and multiplying by 4, the average porewidth is determined. Two different techniques are employed for porewidth determination—the BET value and the BJH value. For bothtechniques, the C5 epoxy sample cured at 35% humidity showed a largerpore width than the C5 epoxy cured with 0% humidity (25.53 as opposed to0.312 nm with BET, 39.53 as opposed to 27.16 nm with BJH). The inclusionof water during the B-stage curing appears to provide a larger porestructure in the cured epoxy-based polymer. Based on the BET porewidths, a smaller pore width, for example, given by curing in 0%humidity, provides the ability to greatly enhance retention of thelarger triptycene molecule.

The identification and characterization of the starting materialchemistry for the epoxy-based system is included herein, as are theproperties of the cured epoxy-based system. For the C5 epoxy, Part Aepoxy resin has the six components listed above, including the twoproprietary epoxy resins and a proprietary elastomeric polymer; Part Bhas a single a proprietary imidazole hardener, and Part C is an optionalcomponent for colorant and includes nine components, including threeproprietary epoxy resins and a proprietary elastomer. Analysis of thematerials indicates that the hardener of Part B is2-ethyl-4-methyl-1H-imidazole. Of the six components listed for the PartA precursor, the silica and titanium dioxide are believed to berelatively inert and do not play a significant role in the cured epoxychemistry. The neopentyl glycol diglycidyl ether (CAS #17557-23-2) ofPart A has two epoxide groups, so it does not reduce the crosslinkdensity and is believed to provide structural flexibility in between thelarger, more rigid aromatic epoxy resins. This increased mobility allowsthe material to desirably flow and increases the pot life. The twoproprietary epoxy resins are major constituents of the Part A precursor.The elastomeric polymer is not believed to react with the epoxies duringcuring, although unsaturated double bonds may participate in somecross-linking. Generally, where the elastomeric polymer does not react,it forms a separate phase within the epoxy which provides more impactresistance and increased mobility. While not limiting the presentdisclosure to any particular theory, it is likely this elastomericpolymer and the inclusion of the neopentyl glycol diglycidyl ether inthe backbone of the epoxy are imparting the high temperature reflowcapability of the C5 system. The two remaining Part A epoxy resinprecursors are determined to be derivatives of the diglycidyl ether ofBisphenol A.

In the manner, the present teachings provide high-temperature thermalcutoff devices and methods of making such devices, by forminghigh-temperature stable seals and high temperature thermal pelletscomprising one or more organic compounds that are substantially retainedby the seal barrier. The HTTCOs are highly stable, robust, and arecapable of use as switching devices in a variety of high-temperatureapplications that were previously not possible, such as high-temperatureclothing and hair styling irons.

1. A high-temperature pellet composition for use in athermally-actuated, current cutoff device, the pellet compositioncomprising triptycene, wherein the pellet composition maintains itsstructural rigidity up to a transition temperature of about 240° C. 2.The high-temperature pellet composition of claim 1, wherein thetriptycene is present at greater than or equal to about 96% by weight ofthe total pellet composition.
 3. The high-temperature pellet compositionof claim 1, wherein the triptycene is present at greater than or equalto about 99% by weight of the total pellet composition.
 4. Thehigh-temperature pellet composition of claim 1, further comprising oneor more components selected from the group consisting of: a binder, apress aid, a release agent, a pigment, and combinations thereof.
 5. Thehigh-temperature pellet composition of claim 1 consisting essentially oftriptycene and one or more components cumulatively present at greaterthan 0% to less than or equal to about 10% by weight of the pelletcomposition, wherein the one or more components are selected from thegroup consisting of: binders, lubricants, press-aids, pigments, andcombinations thereof.
 6. The high-temperature pellet composition ofclaim 1 consisting essentially of triptycene.
 7. A method of making athermally-actuated, current cutoff device, comprising disposing thehigh-temperature pellet composition of claim 1 in a thermally-actuated,current cutoff device and sealing one or more openings in thethermally-actuated, current cutoff device with a high-temperaturesealant material comprising a cured epoxy resin.
 8. A high-temperaturematerial system for a thermally-actuated, current cutoff device, thehigh-temperature material system comprising: a pellet compositioncomprising a single polycrystalline organic compound selected from thegroup consisting of: triptycene and 1-aminoanthroquinone, wherein thepellet composition maintains its structural rigidity up to a transitiontemperature of about 240° C.; and a high-temperature seal comprising anepoxy resin that is cured and creates a barrier that interacts with thepellet composition to substantially prevent escape of the pelletcomposition into an external environment up to the transitiontemperature.
 9. The high-temperature material system of claim 8, whereinthe single crystalline organic compound comprises triptycene.
 10. Thehigh-temperature material system of claim 8, wherein the singlecrystalline organic compound comprises 1-aminoanthroquinone.
 11. Thehigh-temperature material system of claim 8, wherein the epoxy resin ofthe high-temperature seal is formed from a precursor comprisingbisphenol A.
 12. The high-temperature material system of claim 8,wherein the high-temperature seal is formed from the precursorcomprising a diglycidyl ether bisphenol A resin and a hardenercomprising a modified imidazole compound.
 13. The high-temperaturematerial system of claim 12, wherein the hardener comprises2-ethyl-4-methyl-1H-imidazole.
 14. The high-temperature material systemof claim 12, wherein the high-temperature seal is formed by combining atleast two precursors, wherein a first precursor comprises at least onebisphenol A diglycidyl ether, an elastomer, and neopentyl glycoldiglycidyl ether; and a second precursor comprises2-ethyl-4-methyl-1H-imidazole.
 15. The high-temperature material systemof claim 12, wherein the high-temperature seal is formed by combining atleast three precursors, wherein a first precursor comprises a bisphenolA diglycidyl ether polymer; a second precursor comprises1-(2-cyanoethyl)-2-ethyl-4-methyl imidizole; and a third precursorcomprises benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalicanhydride, and phthalic anhydride.
 16. A high-temperature materialsystem for a thermally-actuated, current cutoff device, thehigh-temperature material system comprising: a pellet compositioncomprising triptycene, wherein the pellet composition maintains itsstructural rigidity up to a transition temperature of about 240° C.; anda high-temperature seal comprising an epoxy resin formed from abisphenol A precursor that is cured and creates a barrier that interactswith the pellet composition to substantially prevent escape of thepellet composition into an external environment up to the transitiontemperature.
 17. The high-temperature material system of claim 16,wherein the epoxy resin comprises a diglycidyl ether bisphenol A resin.18. The high-temperature material system of claim 16, wherein thehigh-temperature seal comprises further comprises a hardener comprisinga modified imidazole compound.
 19. A high-temperature material systemfor a thermally-actuated, current cutoff device, the material systemcomprising: a pellet composition consisting essentially of: a singleorganic polycyclic compound present at greater than or equal to about90% to less than or equal to about 100% by weight by of the pelletcomposition; and one or more additives cumulatively present at greaterthan 0% by weight to less than or equal to about 10% by weight of thepellet composition, wherein the one or more additives are selected fromthe group consisting of: binders, lubricants, press-aids, colorants, andcombinations thereof; wherein the pellet composition maintains itsstructural rigidity up to a transition temperature of about 240° C.; anda high-temperature seal comprising an epoxy resin formed from abisphenol A precursor that is cured and creates a barrier that interactswith the pellet composition to substantially prevent escape of thepellet composition into an external environment up to the transitiontemperature.
 20. The high-temperature material system of claim 19,wherein a binder is present in the pellet composition at greater than orequal to 0% to less than or equal to about 10% by weight, a lubricant orpress aid is present in the pellet composition at greater than or equalto 0% to less than or equal to about 5% by weight of the pelletcomposition, and a pigment is present in the pellet composition atgreater than or equal to 0% to less than or equal to about 2% by weightof the pellet composition.
 21. The high-temperature material system ofclaim 20, wherein the single organic polycyclic compound is triptyceneor 1-aminoanthroquinone.
 22. A method of making a high-temperaturematerial system for a thermally-actuated, current cutoff device,comprising: preparing a high-temperature pellet composition comprising asingle organic crystalline compound selected from the group consistingof: triptycene and 1-aminoanthroquinone, so that the solid thermalpellet composition maintains its structural rigidity up to about 240°C.; disposing the high-temperature pellet composition into thethermally-actuated, current cutoff device; combining at least twodistinct curable polymeric precursors, wherein at least one of the atleast two distinct curable polymeric precursors is a curable epoxyresin; applying the at least two distinct curable polymeric precursorsto one or more openings of the thermally-actuated, current cutoffdevice; and curing the at least two distinct curable polymericprecursors to form a high-temperature seal comprising the epoxy resinthat creates a barrier that interacts with the pellet composition tosubstantially prevent escape of the pellet composition into an externalenvironment up to the transition temperature.